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Article

Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex

by
Ningwen Yang
1,
Yijia Chang
1,
Jiangyue Wang
1,
David James Young
2,
Hong-Xi Li
1,
Yuxin Lu
1,* and
Zhi-Gang Ren
1,*
1
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2
James Watt School of Engineering, University of Glasgow, University Avenue, Glasgow G12 8QQ, UK
*
Authors to whom correspondence should be addressed.
Molecules 2025, 30(9), 2011; https://doi.org/10.3390/molecules30092011
Submission received: 22 March 2025 / Revised: 29 April 2025 / Accepted: 29 April 2025 / Published: 30 April 2025
(This article belongs to the Special Issue Inorganic Chemistry in Asia)
Browse Figures
Versions Notes

Abstract

:
A binuclear Au-P complex [Au2(2-bdppmapy)2](PF6)2 (1) was synthesised by the reaction of 2-bdppmapy (N,N′-bis-(diphenylphosphanylmethyl-2-aminopyridine) with AuCN and [Cu(MeCN)4]PF6. The solid phase of 1 emitted bright yellow phosphorescence at λmax = 580 nm under UV excitation (QY = 4.41%, τ = 1.88 μs), which shifted to green (λmax = 551 nm, QY = 5.73%) after being pressurised under 5 MPa. This colour change was recoverable upon exposure to CH2Cl2 vapor. Similar mechanochromic photoluminescence behaviour was observed after grinding the crystals of 1. A filter paper impregnated with 1 demonstrated recyclable write/erase functionality for encrypted information transfer.

1. Introduction

Stimuli-responsive complexes with tuneable photoluminescence (PL) have gained considerable attention in recent years [1,2,3,4,5] due to their potential applications as sensors [6,7,8], PL switches [9,10,11], and data storage devices [12,13,14]. Upon exposure to external stimuli, these complexes exhibited visible colour changes in emission, which can be induced by light [15,16,17], electrical current [18,19,20], heat [21,22,23,24], solvent [25,26,27], and mechanical force [28,29,30,31,32,33,34,35,36]. Mechanochromic photoluminescence, a phenomenon where mechanical force alters the emission colour [37,38,39], has been attributed to changes in molecular arrangement [29,40,41], conformational flexibility [42,43], or altered intermolecular interactions [44,45,46]. A number of gold, silver, and platinum complexes emit bright PL in the solid state, and their emission energies can be tuned by variations in metal–ligand coordination bonds, metal–metal interactions, and weak interactions such as van der Waals forces and hydrogen bonds [47,48,49,50,51]. Over the past decades, these complexes have emerged as attractive stimuli-responsive mechanochromic PL materials. For example, an anthryl Au(I) isocyanide complex demonstrated a bathochromic shift in emission from the visible to infrared region upon grinding, attributed to enhanced intermolecular aurophilic interactions [52].
The mechanochromic PL of complexes is most commonly induced by grinding. Under static high pressures (GPa-level), some Cu-N and Pt-N complexes exhibit chromic PL, which recovers to original colours when the pressures are released [53,54,55]. Determining the precise origin of mechanochromic PL is challenging due to the loss of crystallinity complicating solid-state structural characterisation, even though Ito and coworkers reported novel mechano-force-triggered luminescence in Au complexes arising from single-crystal-to-single-crystal domino transformations, while a minor mechano-stimulus is required to trigger the PL [34,35,56].
Various Au(I) complexes with phosphine ligands have exhibited stimuli-responsive PL toward vapor, ions, solvent, and mechano-forces [57,58,59,60], and this has encouraged us to explore the PL behaviours of Au(I) with some hybrid phosphine ligands containing –PPh2 groups and other donors such as –Py, –phen, –Pz, C=S, and –C≡CH groups [61,62,63], as the secondary donor group may supply additional sites for coordination and non-covalent interactions that activating the changing over PL. For example, we recently reported that a Au-P-S complex exhibited switchable PL upon grinding, related to the collapse and restoration of the crystalline phase accompanied by the disruption and reforming of intermolecular hydrogen bonds. However, this PL did not change after being treated under static pressure up to 12 MPa [62]. In the current work, we carried out the reaction of the PNP-type ligand 2-bdppmapy (N,N-bis-(diphenylphosphanylmethyl-2-aminopyridine) with AuCN and [Cu(MeCN)4]PF6, intended to generate some heterometallic Au/Cu complexes with good PL responses. Unexpectedly, this reaction lead to the formation of a new complex [Au2(2-bdppmapy)2](PF6)2 (1), which contains only two Au(I) metal centres in the structure. The PL of 1 in the solid state changes from yellow to green induced by static pressures as low as 2.5 MPa and can be recovered by exposure to CH2Cl2 vapor, making it suitable for encrypted information transfer.

2. Results and Discussion

2.1. Synthesis and Characterisation

Crystals of 1·EtOH were isolated from the reaction of 2-bdppmapy, AuCN, and [Cu(MeCN)4]PF6 (molar ratio 1:1:1) in CH2Cl2/EtOH at room temperature followed by the diffusion of petroleum ether and Et2O into the reaction mixture (Scheme 1). The driving force for this metathesis was the precipitation of insoluble CuCN. Changing the ratios and salts did not improve the yield.
The EtOH solvent molecules were eliminated quickly from the crystal of 1·EtOH and resulted in solventless 1 in 58% yield. Compound 1 was stable in air and water, soluble in MeCN, DMF, and DMSO, partially soluble in CH2Cl2, CHCl3, MeOH, and EtOH, and insoluble in other common solvents. Elemental analysis of 1 was consistent with its chemical formula. The TGA curve of 1 (Figure S1) revealed that it had no EtOH solvent molecules at room temperature. It was thermally stable below 250 °C, and subsequently lost its organic components at higher temperatures. The PXRD pattern of 1 generally matched that simulated from the single-crystal X-ray diffraction (SCXRD) data of 1·EtOH, indicating the main cell parameters remained, whereas the intensity of some peaks varied due to the elimination of EtOH molecules (Figure S2). The IR spectrum of 1 (Figure S3) contained signals attributable to the stretching vibrations of the –Ph and –Py groups at 1591, 1475, 1435, 775, 733, and 691 cm−1; of the –CH2– group at 1475 cm−1; and of the PF6− anion at 829 cm−1, while that of 1·EtOH showed the peaks of the lattice EtOH molecule at 3344 cm−1 (–OH), 2976, and 2880 cm−1 (–C2H5). The 1H NMR spectrum of 1 in DMSO-d6 (Figure S4) consisted of signals assignable to the –CH2– group (4.22 ppm) and the –Py and –Ph groups (8.06–6.57 ppm). The 31P{H} NMR spectrum contained a single resonance at 44.66 ppm.
SCXRD analysis of 1·EtOH at 223 K revealed that it crystallised in the space group P21/n. Each asymmetric unit contains half of the [Au2(2-bdppmapy)2]2+ dication, one PF6− anion, and half of the EtOH molecule. Two Au atoms and two 2-bdppmapy molecules are bonded head-to-head to form a distorted Au2P4 quadrilateral structure (Figure 1). The Au1 atom is coordinated with two –PPh2 groups with the P–Au–P bond angle of 174.37(8)°. The mean Au-P bond length is 2.309(2) Å. The distance between Au1 and Au1A (4.550 Å) confirms the absence of an aurophilic interaction.

2.2. Photophysical Properties

The PL responses of 1 in the solid state and in solution at room temperature were recorded (Figure 2). Upon excitation at λmax = 345 nm, a solid sample of 1 emitted yellow (λmax = 580 nm) with a quantum yield (QY) of 4.41%. The microsecond lifetime (τ = 1.88 μs, excited at 370 nm, measured by transient PL) indicated phosphorescent emission. By comparison, solutions of 1 in MeCN, DMSO, and DMF were non-emissive, likely due to the interactions between 1 and these polar solvents, as well as free rotation of the –Ph groups in solutions that facilitate non-radiative relaxation of the excited state.
Density functional theory (DFT) calculations based on the SCXRD data of 1 were employed to calculate the frontier orbital distributions. As shown in Figure 3, the HOMOs were mainly located at the π orbitals of the –Py group. The LUMO was delocalised over the Au–P bond, while the LUMO+1 was mainly located at the π* orbitals of the –Ph group. The PL of compound 1 is likely due to ligand-to-metal charge transfer (3LMCT) combined with intra-ligand charge transfer (3ILCT) [64,65].

2.3. Pressure-Induced Mechanochromic Photoluminescence

We investigated the PL of five samples of 1 after exposure to different pressures (1—1 MPa, 1—2.5 MPa, 1—5 MPa, 1—10 MPa, 1—20 MPa) for 10 min (Figure 4a). The emission λmax of 1 remained unchanged in response to low pressure (1—1 MPa, 580 nm), but shifted to shorter wavelengths in response to higher pressures (1—2.5 MPa, λmax = 573 nm; 1—5 MPa, λmax = 551 nm; 1—10 MPa, λmax = 547 nm; and 1—20 MPa, λmax = 547 nm). Accompanied with a slightly enhanced QY (5.73% for 1—5 MPa), this yellow-to-green colour change was visible to the naked eye (Figure 4b,c).
PXRD patterns were obtained to examine the phase transition of 1 in response to pressure. In the PXRD patterns of 1—5 MPa, 1—10 MPa, and 1—20 MPa, the major peaks at 2θ = 8.3° (h, k, l = 0, 1, 1), 8.6° (h, k, l = 1, 0, 1), 9.8° (h, k, l = 1, 1, 0) vanished, while peaks at 8.5°, 8.8° and 9.9° appeared. The changing on PXRD peaks indicated the change in interplanar crystal spacing distances and the forming of a new crystalline phase. By comparison, the PXRD pattern of 1—2.5 MPa contained peaks corresponding to both phases, demonstrating incomplete phase-transition. In the case of 1—1 MPa, weak signals at 8.9° and 9.0° were also observable, illustrating that this phase transition could occur slightly even at low pressure.
Since the changes in the emission spectra and PXRD patterns were almost complete after 10 min at 5 MPa, we used this sample as a model. When 1—5 MPa was exposed to CH2Cl2 vapor for 5 min, the resulting solid (1r) emitted at 582 nm, almost identical to the PL of 1. Likewise, the PXRD pattern of 1r showed peaks at 2θ = 8.4°, 8.7°, and 9.8°, again almost identical to 1 (Figure 4a,c). This cycle of pressure and exposure to CH2Cl2 vapor was repeated five times without noticeable changes in the PL wavelengths of the two phases (Figure S5).
When 1 was ground in a mortar, the emission of the resulted solid 1g blue-shifted to λmax = 557 nm, in-between the wavelengths of 1—2.5 MPa and 1—5 MPa (Figure 4a), indicating that grinding had less of a mechanochromic PL effect than pressure at 5 MPa. When 1g was exposed to CH2Cl2 vapor, the emission of the resulted solid (1gr) also recovered to λmax = 580 nm. Although the PXRD patterns of 1g and 1gr were less crystalline, some peaks were observable. The PXRD pattern of 1g showed peaks at 2θ = 8.5°, 8.7°, and 9.9°, which recovered to 2θ = 8.5°, 8.7°, and 9.8° in 1gr. These emission spectra and PXRD patterns indicated that the phase transition induced by grinding was broadly similar to that induced by static pressure.
To explain these phase transitions, we investigated the SCXRD data and calculated that there was a total void of 204.2 Å3 in each cell (Figure S6, 6.3% of cell volume, calculated using PLATON v1.18) in the crystal structure of 1. We then performed nitrogen adsorption/desorption experiments which indicated that the pore volume of 1 (0.042 cm3/g) was reduced to nearly half in 1—5 MPa (0.021 cm3/g), and was restored in 1r (0.047 cm3/g). We therefore concluded that pressure reduced the void in the crystal structure in 1, and CH2Cl2 molecules then inserted into the voids and restored the unit cell, which has been observed in other mechanochromic Au complexes [66,67,68]. Examination of the SCXRD data also indicated various C–H···F hydrogen bonds (Table 1 and Figure 5a) between the [Au2(2-bdppmapy)2]2+ dication and the PF6− anions, and a number of intra- and inter-molecular C–H···π interactions (Table 2 and Figure 5b) between neighbouring [Au2(2-bdppmapy)2]2+ dications.
We examined the Hirshfeld surfaces to quantify the contribution of non-covalent interactions in the crystal packing. The software Multiwfn v3.8 [69] was used for the analysis of the Hirshfeld surface. As shown in the coloured map of dnorm (Figure 6), the red-coloured regions signified the presence of the aforementioned hydrogen bonds and C–H···π interactions, which were consistent with the results obtained from PLATON calculations.
Comparing the IR spectra of 1 and 1—5 MPa (Figure 7), the characteristic absorption of PF6− at 829 cm−1 remained unchanged. However, the signals for the –Ph and –Py groups at 1506 cm−1 distinctly weakened in the latter, and some new weak signals at 1558, 1541, 1520, and 1506 cm−1 appeared. These IR spectral data suggest that during mechanical pressuring, the hydrogen bonding environment of the PF6− anion was minimally affected, whereas the chemical environment around the –Ph and –Py groups was significantly affected. These spectral changes were restored in 1r, consistent with the restoration of the emission spectra. To this end, we propose that pressure mostly disrupts the C–H···π interactions associated with the –PPh2 and –Py groups, thereby altering the emission of 1 in the solid state.

2.4. Application to Encrypted Information Transfer

This responsiveness of the PL of complex 1 to external stimuli was used to make invisible ink [70]. Compound 1 was impregnated on filter paper and activated by CH2Cl2 vapor. Writing on a thin cover paper placed over the filter paper using an inkless ball-point pen (Figure 8) at normal writing strength did not produce a noticeable change under natural light. However, writing appeared under UV light at 365 nm, and could be erased by exposure to a CH2Cl2 atmosphere for 5 min. This write/erase operation could be repeated several times and endowed compound 1 as an encrypted information transformation material.

3. Experimental Section

3.1. Materials, Characterisation, and Measurements

2-Bdppmapy was prepared using a method from the literature [71]. All other materials were supplied from commercial sources and used as received. Elemental analyses were performed on a Thermal Fisher Flash Smart microanalyzer (Thermo Fisher Scientific, Waltham, MA, USA). Powder X-ray diffraction (PXRD) patterns were recorded on a Bruker D2 Phaser X-ray diffractometer (Bruker, Billerica, MA, USA) with the Bragg–Brentano method using a Cu Kα source (30 kV, 10 mA). IR spectra were acquired on a Bruker VERTEX 70 FT-IR spectrometer (4000–600 cm−1) (Bruker, Billerica, MA, USA) with an ATR probe. Thermogravimetric analysis (TGA) was performed on a TA SDT-2960 analyser (TA Instruments, New Castle, DE, USA) from room temperature to 800 °C under a N2 stream, with a heating rate of 10 °C /min. NMR spectra were acquired on a Bruker AVANCE NEO NMR spectrometer (Bruker, Billerica, MA, USA). N2 adsorption/desorption experiments were conducted using a Belsorp-Max gas adsorption analyser (Microtrac BEL, Osaka, Japan). Emission spectra, transient photoluminescence, and QY measurements were performed on an Edinburgh FLS1000 spectrometer (Edinburgh Instruments, Livingston, UK).

3.2. Synthesis of [Au2(2-Bdppmapy)2](PF6)2 (1)

A mixture of CH2Cl2/EtOH (v/v = 1:1, 6.0 mL), AuCN (8.92 mg, 0.04 mmol), and 2-bdppmapy (19.6 mg, 0.04 mmol) was stirred at room temperature for 6 h, followed by the addition of [Cu(MeCN)4]PF6 (14.6 mg, 0.04 mmol) and more stirring for 5 min. The resulting suspension was then filtered, and the filtrate was diffused with petroleum ether and Et2O (1:1). [Au2(2-bdppmapy)2](PF6)2·EtOH (1·EtOH) was isolated as colourless crystals after 2 days, which were collected, washed with Et2O, and dried in air. Yield for 1: 76.7 mg (58% based on Au). Anal. Calcd for C62H56Au2F12N4P6: C, 44.73; H, 3.39; N, 3.37; found: C, 43.93; H, 3.70; N, 3.24 (%). IR (ATR, cm−1): 1591 (m), 1566 (w), 1476 (m), 1435 (s), 1283 (w), 1221 (m), 1159 (w), 1099 (m), 829 (vs), 775 (m), 733 (s), 691 (s). 1H NMR (400 MHz, DMSO-d6, ppm): δ 8.06 (dd, J = 4.9, 1.3 Hz, 2H), 7.44–7.36 (m, 42 H), 6.75 (d, J = 8.6 Hz, 2H), 6.57 (dd, J = 6.9, 5.0 Hz, 2H), 4.22 (d, J = 2.4 Hz, 8H). 13C NMR (101.6 MHz, DMSO-d6, ppm): δ 156.62, 147.20, 137.15, 136.97, 132.98, 132.89, 132.79, 128.93, 128.62, 128.59, 128.56, 112.12, 107.40, 49.82 ppm. 31P{H} NMR (162 MHz, DMSO-d6, ppm): δ 44.66.

3.3. Preparations of 1—1 MPa, 1—2.5 MPa, 1—5 MPa, 1—10 MPa, 1—20 MPa, and 1g

A mould (Φ = 9 mm) containing 3 mg of 1 was subjected to pressures of 1 MPa, 2.5 MPa, 5 MPa, 10 MPa, and 20 MPa (hand press) for 10 min each. The pressure was then released and the pellets collected (1—1 MPa was collected as a powder due to the low pressure). Compound 1g was prepared by grinding 1 (3 mg) in a mortar for more than 5 min.

3.4. Preparations of 1r and 1gr

Samples of 1-5 MPa and 1g were placed in a small beaker (5 mL), and sealed with 5 mL of CH2Cl2 in a 50 mL beaker for 5 min, respectively.

3.5. Preparation of ‘Secret Writing Paper’

Powdered 1 (3 mg) was plastered onto a small filter paper (Φ = 9 mm). This ‘secret writing paper’ was exposed to CH2Cl2 vapor for 5 min to activate it before use.

3.6. Single-Crystal X-Ray Diffraction (SCXRD) Determination

A single crystal of 1·EtOH (0.30 mm × 0.30 mm × 0.10 mm) was selected directly from the synthesis. SCXRD measurements were performed on an Agilent Xcalibur diffractometer (Agilent, Santa Clara, CA, USA) using Mo Kα (λ = 0.71073 Å) radiation at 223 K. The diffraction data were collected and refined, and a multi-scan absorption correction was applied using CrysAlisPro 1.171.42.81a. The structure was solved by direct methods using SHELXS (Sheldrick, 2016/6) and refined by full-matrix least-squares methods against F2 using SHELXL (Sheldrick, 2016/6) [72]. The PF6− anion was disordered over two sites rotating along the F1-P3-F2 axis with occupancies of 0.50/0.50 for F3-F6/F3A-F6A. The EtOH mole was disordered at opposite positions with equal (0.5/0.5) occupancies. The disordered F atoms at the PF6− anion and the C and O atoms of the disordered EtOH molecule were refined isotropically, while all other non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed at calculated positions and constrained to ride over their parent C and N atoms. Selected crystallographic data and refinement parameters are listed in Table S1.

3.7. Computational Details

Theoretical calculations were conducted using the Gaussian 16-C01 software package at the B3LYP-GD3BJ/def2SVP level [73]. Based on the crystal structure, we froze the heavy atoms in the optimisation and optimised the hydrogen atoms.

4. Conclusions

In summary, we have synthesised a binuclear Au-P complex [Au2(2-bdppmapy)2](PF6)2 (1), which emitted yellow phosphorescence in the solid state at λmax = 580 nm upon 345 nm excitation. DFT calculations suggested that this PL is attributable to a combination of 3LMCT and 3ILCT. Induced by pressures as low as 2.5 MPa, the emission of 1 visibly shifted from yellow to green. The PXRD pattern changes indicated a clear phase transition, observable at 1 MPa and completed at pressures exceeding 5 MPa. This emission change could be recovered by exposure to CH2Cl2 vapor, and these reversible transformations could be cycled multiple times. The mechanochromic PL behaviour of 1 was likely associated with the reducing of voids in the unit cell, which altered the inter- and intra-molecular C–H···π interactions, perturbed electron densities over the –PPh2 and –Py groups, and varied energy gaps between the excited and ground states. Furthermore, a ‘secret writing paper’ impregnated with complex 1 was utilised to make invisible ink that can be seen under UV light and erased upon exposure to CH2Cl2 vapor. This work presented an example of a novel recoverable mechanochromic PL material suitable for force-sensitive sensors. Additionally, our laboratory is actively exploring other stimuli-responsive photoluminescent complexes.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/molecules30092011/s1, Figure S1: TGA curve of 1; Figure S2: PXRD patterns of as-synthesised 1 and those simulated from the SCXRD data; Figure S3: IR spectra of 1 and 1·EtOH; Figure S4: 1H, 13C, and 31P{1H} NMR spectra of 1 in DMSO-d6; Figure S5: Emission spectra and maximum wavelength of the emission spectra of 1 during the 5-round pressure-vapor cycles; Figure S6: Packing diagram indicating the void in 1; Table S1: Selected crystallographic data and refinement parameters for 1. Cartesian coordinates of molecule 1.

Author Contributions

Z.-G.R. administrated the project, made the data curation, and wrote the original draft. N.Y., Y.C. and J.W. conducted formal analysis, investigation, and data curation. Y.L. performed the computational calculations. H.-X.L. undertook investigation and data curation. D.J.Y. reviewed data and edited the manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21671144).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The crystallographic data are available from the Cambridge Crystallographic Data Centre (CCDC number 2419373). Other data not presented in the Supplementary Materials are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Jin, M.; Ito, H. Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties. J. Photochem. Photobiol. C 2022, 51, 100478. [Google Scholar] [CrossRef]
  2. Tong, Y.; Chen, X.-W.; He, L.-H.; Chen, J.-L.; Liu, S.-J.; Wen, H.-R. Reversible stimuli-responsive luminescence of bimetallic cuprous complexes based on NH-deprotonated 3-(2′-pyridyl)pyrazole. J. Mater. Chem. C 2021, 9, 16664–16671. [Google Scholar] [CrossRef]
  3. Yang, D.-D.; Xiao, T.; Yang, Y.-Y.; Xue, J.-H.; Shi, Y.-S.; Ma, Q.; Zheng, X.-J. Two viologen-based complexes as persistent luminescent materials and their applications in inkless print and anticounterfeiting. Chem. Eng. J. 2024, 488, 151047. [Google Scholar] [CrossRef]
  4. Wei, Z.; Zhang, K.; Kim, C.K.; Tan, S.; Wang, S.; Wang, L.; Li, J.; Wang, Y. Stimuli-responsive cyclometalated platinum complex bearing bent molecular geometry for highly efficient solution-processable OLEDs. Chin. Chem. Lett. 2021, 32, 493–496. [Google Scholar] [CrossRef]
  5. Takeda, H.; Kobayashi, A.; Tsuge, K. Recent developments of photoactive Cu(I) and Ag(I) complexes with diphosphine and related ligands. Coord. Chem. Rev. 2022, 470, 214700. [Google Scholar] [CrossRef]
  6. Kumar, P.; Kaushik, R.; Ghosh, A.; Jose, D.A. Detection of Moisture by Fluorescent OFF-ON Sensor in Organic Solvents and Raw Food Products. Anal. Chem. 2016, 88, 11314–11318. [Google Scholar] [CrossRef]
  7. Lv, C.-L.; Yang, C.-H.; Liu, L.-Y.; Zhang, Z.-C. Organoimido functionalized trinuclear gold(I) clusters with fluorescent chromophore. Rare Met. 2020, 40, 1437–1442. [Google Scholar] [CrossRef]
  8. Lee, L.C.; Lo, K.K. Shining New Light on Biological Systems: Luminescent Transition Metal Complexes for Bioimaging and Biosensing Applications. Chem. Rev. 2024, 124, 8825–9014. [Google Scholar] [CrossRef]
  9. Seki, T.; Takamatsu, Y.; Ito, H. A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions. J. Am. Chem. Soc. 2016, 138, 6252–6260. [Google Scholar] [CrossRef]
  10. Qin, Y.; She, P.; Huang, X.; Huang, W.; Zhao, Q. Luminescent manganese(II) complexes: Synthesis, properties and optoelectronic applications. Coord. Chem. Rev. 2020, 416, 213331. [Google Scholar] [CrossRef]
  11. Li, Y.; Chen, L.; Ai, Y.; Hong, E.Y.; Chan, A.K.; Yam, V.W. Supramolecular Self-Assembly and Dual-Switch Vapochromic, Vapoluminescent, and Resistive Memory Behaviors of Amphiphilic Platinum(II) Complexes. J. Am. Chem. Soc. 2017, 139, 13858–13866. [Google Scholar] [CrossRef] [PubMed]
  12. Gao, M.; Li, J.; Peng, N.; Jiang, L.; Zhao, S.; Fu, D.-Y.; Li, G. Multi-stimuli responsive lanthanides-based luminescent hydrogels for advanced information encryption. J. Mol. Liq. 2022, 368, 120681. [Google Scholar] [CrossRef]
  13. Xiao, Z.-M.; Yang, J.-X.; Chen, X.; Tang, W.-J.; Peng, S.-K.; Hao, D.-B.; Zhao, Z.-P.; Zheng, J.; Li, D. A fluorescence–phosphorescence dual-emissive Cu3(pyrazolate)3 complex with highly tunable emission colours for anticounterfeiting and temperature sensing. Inorg. Chem. Front. 2024, 11, 1808–1818. [Google Scholar] [CrossRef]
  14. Yang, H.; Peng, S.K.; Zheng, J.; Luo, D.; Xie, M.; Huang, Y.L.; Cai, X.; Wang, J.; Zhou, X.P.; Li, D. Achiral Au(I) Cyclic Trinuclear Complexes with High-Efficiency Circularly Polarized Near-Infrared TADF. Angew. Chem. Int. Ed. 2023, 62, e202310495. [Google Scholar] [CrossRef]
  15. Wu, N.M.; Ng, M.; Yam, V.W. Photochromic Benzo[b]phosphole Alkynylgold(I) Complexes with Mechanochromic Property to Serve as Multistimuli-Responsive Materials. Angew. Chem. Int. Ed. 2019, 58, 3027–3031. [Google Scholar] [CrossRef]
  16. Wu, N.M.; Ng, M.; Yam, V.W. Photocontrolled multiple-state photochromic benzo[b]phosphole thieno[3,2-b]phosphole-containing alkynylgold(I) complex via selective light irradiation. Nat. Commun. 2022, 13, 33. [Google Scholar] [CrossRef]
  17. Rolz, M.; Butschke, B.; Breit, B. Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis. J. Am. Chem. Soc. 2024, 146, 13210–13225. [Google Scholar] [CrossRef]
  18. Pi, Q.; Bi, D.; Qiu, D.; Wang, H.; Cheng, X.; Feng, Y.; Zhao, Q.; Zhou, M. A dual-wavelength electrochromic film based on a Pt(II) complex for optical modulation at telecommunication wavelengths and dark solid-state display devices. J. Mater. Chem. C 2021, 9, 8994–9000. [Google Scholar] [CrossRef]
  19. Banasz, R.; Wałęsa-Chorab, M. Polymeric complexes of transition metal ions as electrochromic materials: Synthesis and properties. Coord. Chem. Rev. 2019, 389, 1–18. [Google Scholar] [CrossRef]
  20. Sun, N.; Zhang, S.T.; Simon, F.; Steiner, A.M.; Schubert, J.; Du, Y.; Qiao, Z.; Fery, A.; Lissel, F. Poly(3-hexylthiophene)s Functionalized with N-Heterocyclic Carbenes as Robust and Conductive Ligands for the Stabilization of Gold Nanoparticles. Angew. Chem. Int. Ed. 2021, 60, 3912–3917. [Google Scholar] [CrossRef]
  21. Brown, C.M.; Carta, V.; Wolf, M.O. Thermochromic Solid-State Emission of Dipyridyl Sulfoxide Cu(I) Complexes. Chem. Mater. 2018, 30, 5786–5795. [Google Scholar] [CrossRef]
  22. Artem’ev, A.V.; Ryzhikov, M.R.; Berezin, A.S.; Kolesnikov, I.E.; Samsonenko, D.G.; Bagryanskaya, I.Y. Photoluminescence of Ag(I) complexes with a square-planar coordination geometry: The first observation. Inorg. Chem. Front. 2019, 6, 2855–2864. [Google Scholar] [CrossRef]
  23. Stal, S.; Huitorel, B.; Coustham, T.; Stephant, N.; Massuyeau, F.; Gacoin, T.; Bouteiller, L.; Perruchas, S. Photoactive CuI-Cross-Linked Polyurethane Materials. ACS Appl. Mater. Interfaces 2022, 14, 47931–47940. [Google Scholar] [CrossRef]
  24. Artem’ev, A.V.; Rogovoy, M.I.; Odud, I.M.; Davydova, M.P.; Rakhmanova, M.I.; Petrov, P.A.; Brel, V.K.; Artushin, O.I.; Brylev, K.A.; Samsonenko, D.G.; et al. Toward highly efficient TADF-active Cu(I), Ag(I) and Au(I) carbene complexes using symmetry-based design strategy. Inorg. Chem. Front. 2024, 11, 8778–8788. [Google Scholar] [CrossRef]
  25. Soto, M.A.; Carta, V.; Andrews, R.J.; Chaudhry, M.T.; MacLachlan, M.J. Structural Elucidation of Selective Solvatochromism in a Responsive-at-Metal Cyclometalated Platinum(II) Complex. Angew. Chem. Int. Ed. 2020, 59, 10348–10352. [Google Scholar] [CrossRef]
  26. Nagy, M.; Rácz, D.; Nagy, Z.L.; Fehér, P.P.; Kalmár, J.; Fábián, I.; Kiss, A.; Zsuga, M.; Kéki, S. Solvatochromic isocyanonaphthalene dyes as ligands for silver(I) complexes, their applicability in silver(I) detection and background reduction in biolabelling. Sens. Actuators B 2018, 255, 2555–2567. [Google Scholar] [CrossRef]
  27. Seki, T.; Ozaki, T.; Okura, T.; Asakura, K.; Sakon, A.; Uekusa, H.; Ito, H. Interconvertible multiple photoluminescence color of a gold(I) isocyanide complex in the solid state: Solvent-induced blue-shifted and mechano-responsive red-shifted photoluminescence. Chem. Sci. 2015, 6, 2187–2195. [Google Scholar] [CrossRef]
  28. Zhao, X.; Gong, J.; Li, Z.; Sung, H.H.Y.; Williams, I.D.; Lam, J.W.Y.; Zhao, Z.; Tang, B.Z.; Wong, W.Y.; Xu, L. Au···I coinage bonds: Boosting photoluminescence efficiency and solid-state molecular motion. Aggregate 2024, 6, e686. [Google Scholar] [CrossRef]
  29. Li, H.; Yang, J.; Wang, Q.; Tong, H.; Zhu, J.; Liu, W.; Ouyang, G. Ligand Detachment—New Insight into the Mechanochromic Luminescence Mechanism of Copper Iodide Complexes with Thermally Activated Delayed Fluorescence. Adv. Opt. Mater. 2024, 12, 2400364. [Google Scholar] [CrossRef]
  30. Chen, X.-W.; He, L.-H.; Ju, P.; Chen, J.-L.; Liu, S.-J.; Wen, H.-R. Mechanochromic luminescent materials of bimetallic Cu(I) complexes showing thermally activated delayed fluorescence. J. Mater. Chem. C 2020, 8, 16160–16167. [Google Scholar] [CrossRef]
  31. Hashimoto, Y.; Katagiri, Y.; Tanaka, Y.; Yoshizawa, M. Solution-state mechanochromic luminescence of Pt(II)-complexes displayed within micellar aromatic capsules. Chem. Sci. 2023, 14, 14211–14216. [Google Scholar] [CrossRef] [PubMed]
  32. Kwon, E.; Kim, J.; Lee, K.Y.; Kim, T.H. Non-Phase-Transition Luminescence Mechanochromism of a Copper(I) Coordination Polymer. Inorg. Chem. 2017, 56, 943–949. [Google Scholar] [CrossRef] [PubMed]
  33. Deak, A.; Jobbagy, C.; Demeter, A.; Celko, L.; Cihlar, J.; Szabo, P.T.; Abranyi-Balogh, P.; Crawford, D.E.; Virieux, D.; Colacino, E. Mechanochemical synthesis of mononuclear gold(I) halide complexes of diphosphine ligands with tuneable luminescent properties. Dalton Trans. 2021, 50, 13337–13344. [Google Scholar] [CrossRef]
  34. Seki, T.; Sakurada, K.; Ito, H. Controlling mechano- and seeding-triggered single-crystal-to-single-crystal phase transition: Molecular domino with a disconnection of aurophilic bonds. Angew. Chem. Int. Ed. Engl. 2013, 52, 12828–12832. [Google Scholar] [CrossRef]
  35. Ito, H.; Muromoto, M.; Kurenuma, S.; Ishizaka, S.; Kitamura, N.; Sato, H.; Seki, T. Mechanical stimulation and solid seeding trigger single-crystal-to-single-crystal molecular domino transformations. Nat. Commun. 2013, 4, 2009. [Google Scholar] [CrossRef]
  36. Zhang, X.; Wang, J.Y.; Ni, J.; Zhang, L.Y.; Chen, Z.N. Vapochromic and mechanochromic phosphorescence materials based on a platinum(II) complex with 4-trifluoromethylphenylacetylide. Inorg. Chem. 2012, 51, 5569–5579. [Google Scholar] [CrossRef]
  37. Eddingsaas, N.; Suslick, K. Intense Mechanoluminescence and Gas Phase Reactions from the Sonication of an Organic Slurry. J. Am. Chem. Soc. 2007, 129, 6718–6719. [Google Scholar] [CrossRef]
  38. Zhang, X.; Chi, Z.; Zhang, Y.; Liu, S.; Xu, J. Recent advances in mechanochromic luminescent metal complexes. J. Mater. Chem. C 2013, 1, 3376–3390. [Google Scholar] [CrossRef]
  39. Cheng, S.; Chen, Z.; Yin, Y.; Sun, Y.; Liu, S. Progress in mechanochromic luminescence of gold(I) complexes. Chin. Chem. Lett. 2021, 32, 3718–3732. [Google Scholar] [CrossRef]
  40. Chen, W.-T.; Li, C.-H.; Liang, Z.-Y.; Zhang, Z.-L.; Liu, D.-Q.; Ye, J.-W.; Chen, L.; Chen, X.-M. Large and Tunable Wavelength Blue Shifts in Luminescent Piezochromism of Cu(I) Complexes via a Guest Encapsulation Strategy. ACS Mater. Lett. 2024, 6, 2077–2084. [Google Scholar] [CrossRef]
  41. Walters, D.T.; Aghakhanpour, R.B.; Powers, X.B.; Ghiassi, K.B.; Olmstead, M.M.; Balch, A.L. Utilization of a Nonemissive Triphosphine Ligand to Construct a Luminescent Gold(I)-Box That Undergoes Mechanochromic Collapse into a Helical Complex. J. Am. Chem. Soc. 2018, 140, 7533–7542. [Google Scholar] [CrossRef] [PubMed]
  42. Li, W.-B.; Luo, W.-J.; Li, K.-X.; Yuan, W.-Z.; Zhang, Y.-M. Aggregation-induced phosphorescence and mechanochromic luminescence of a tetraphenylethene-based gold(I) isocyanide complex. Chin. Chem. Lett. 2017, 28, 1300–1305. [Google Scholar] [CrossRef]
  43. Zhang, X.; Zhang, L.-Y.; Wang, J.-Y.; Dai, F.-R.; Chen, Z.-N. Two-step phosphorescent mechanochromism due to intramolecular deformation. J. Mater. Chem. C 2020, 8, 715–720. [Google Scholar] [CrossRef]
  44. Zhang, J.; He, B.; Wu, W.; Alam, P.; Zhang, H.; Gong, J.; Song, F.; Wang, Z.; Sung, H.H.Y.; Williams, I.D.; et al. Molecular Motions in AIEgen Crystals: Turning on Photoluminescence by Force-Induced Filament Sliding. J. Am. Chem. Soc. 2020, 142, 14608–14618. [Google Scholar] [CrossRef]
  45. Ai, Y.; Li, Y.; Chan, M.H.; Xiao, G.; Zou, B.; Yam, V.W. Realization of Distinct Mechano- and Piezochromic Behaviors via Alkoxy Chain Length-Modulated Phosphorescent Properties and Multidimensional Self-Assembly Structures of Dinuclear Platinum(II) Complexes. J. Am. Chem. Soc. 2021, 143, 10659–10667. [Google Scholar] [CrossRef]
  46. Balch, A.L. Dynamic crystals: Visually detected mechanochemical changes in the luminescence of gold and other transition-metal complexes. Angew. Chem. Int. Ed. Engl. 2009, 48, 2641–2644. [Google Scholar] [CrossRef]
  47. Kuchison, A.M.; Wolf, M.O.; Patrick, B.O. Conjugated ligand-based tribochromic luminescence. Chem. Commun. 2009, 47, 7387–7389. [Google Scholar] [CrossRef]
  48. Lechner, A.; Gliemann, G. Pressure Effects on the Absorption and Emission of Tetracyanoplatinates(II) in Solution. J. Am. Chem. Soc. 1989, 111, 7469–7475. [Google Scholar] [CrossRef]
  49. Theoretical Studies of the Spectroscopic Properties of [Pt(trpy)C⋮CR]+ (trpy = 2,2′,6′,2′′-Terpyridine; R = H, CH2OH, and C6H5). J. Phys. Chem. A 2005, 109, 8809–8818. [CrossRef]
  50. Grey, J.K.; Butler, I.S.; Reber, C. Pressure-Induced Enhancements of Luminescence Intensities and Lifetimes Correlated with Emitting-State Distortions for Thiocyanate and Selenocyanate Complexes of Platinum(II) and Palladium(II). Inorg. Chem. 2003, 42, 6503–6518. [Google Scholar] [CrossRef]
  51. Rawashdeh-Omary, M.A.; Omary, M.A.; Patterson, H.H.; Fackler, J.P. Excited-State Interactions for [Au(CN)2−]n and [Ag(CN)2−]n Oligomers in Solution. Formation of Luminescent Gold-Gold Bonded Excimers and Exciplexes. J. Am. Chem. Soc. 2001, 123, 11237–11247. [Google Scholar] [CrossRef] [PubMed]
  52. Seki, T.; Tokodai, N.; Omagari, S.; Nakanishi, T.; Hasegawa, Y.; Iwasa, T.; Taketsugu, T.; Ito, H. Luminescent Mechanochromic 9-Anthryl Gold(I) Isocyanide Complex with an Emission Maximum at 900 nm after Mechanical Stimulation. J. Am. Chem. Soc. 2017, 139, 6514–6517. [Google Scholar] [CrossRef] [PubMed]
  53. Xie, M.; Chen, X.R.; Wu, K.; Lu, Z.; Wang, K.; Li, N.; Wei, R.J.; Zhan, S.Z.; Ning, G.H.; Zou, B.; et al. Pressure-induced phosphorescence enhancement and piezochromism of a carbazole-based cyclic trinuclear Cu(I) complex. Chem. Sci. 2021, 12, 4425–4431. [Google Scholar] [CrossRef] [PubMed]
  54. Zhang, Y.; Ni, J.; Zhu, Y.; Zeng, Q.; Ai, Y.; Li, Y. Multi-stimuli responsive Pt(II) complexes for information storage and anti-counterfeiting. Chem. Eng. J. 2024, 498, 155049. [Google Scholar] [CrossRef]
  55. Ono, T.; Tsukiyama, Y.; Taema, A.; Sato, H.; Kiyooka, H.; Yamaguchi, Y.; Nagahashi, A.; Nishiyama, M.; Akahama, Y.; Ozawa, Y.; et al. Piezofluorochromism in Charge-Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding. ChemPhotoChem. 2018, 2, 416–420. [Google Scholar] [CrossRef]
  56. Ito, H.; Saito, T.; Oshima, N.; Kitamura, N.; Ishizaka, S.; Hinatsu, Y.; Wakeshima, M.; Kato, M.; Tsuge, K.; Sawamura, M. Reversible Mechanochromic Luminescence of [(C6F5Au)2(µ-1,4-Diisocyanobenzene)]. J. Am. Chem. Soc. 2008, 130, 10044–10045. [Google Scholar] [CrossRef]
  57. Lim, S.H.; Olmstead, M.M.; Balch, A.L. Molecular accordion: Vapoluminescence and molecular flexibility in the orange and green luminescent crystals of the dimer, Au2(µ-bis-(diphenylphosphino)ethane)2Br2. J. Am. Chem. Soc. 2011, 133, 10229–10238. [Google Scholar] [CrossRef]
  58. Lim, S.H.; Olmstead, M.M.; Balch, A.L. Inorganic topochemistry. Vapor-induced solid state transformations of luminescent, three-coordinate gold(I) complexes. Chem. Sci. 2013, 4, 311–318. [Google Scholar] [CrossRef]
  59. Deák, A.; Jobbagy, C.; Marsi, G.; Molnar, M.; Szakacs, Z.; Baranyai, P. Anion-, Solvent-, Temperature-, and Mechano-Responsive Photoluminescence in Gold(I) Diphosphine-Based Dimers. Chem. Eur. J. 2015, 21, 11495–11508. [Google Scholar] [CrossRef]
  60. Jobbágy, C.; Baranyai, P.; Marsi, G.; Rácz, B.; Li, L.; Naumov, P.; Deák, A. Novel gold(I) diphosphine-based dimers with aurophilicity triggered multistimuli light-emitting properties. J. Mater. Chem. C 2016, 4, 10253–10264. [Google Scholar] [CrossRef]
  61. Hu, S.; Yan, S.; Hu, Y.; Young, D.J.; Li, H.-X.; Lu, C.; He, J.-H.; Ren, Z.-G. A PN(Pz)P ligand protected Au2Cu2 complex for photoluminescent ultra-low humidity detection with reversible single-crystal-to-single-crystal transformations. Inorg. Chem. Front. 2023, 10, 3706–3713. [Google Scholar] [CrossRef]
  62. Huang, J.; Hu, Y.; Xu, W.; Yang, W.; Lu, C.; Young, D.J.; Ren, Z.-G. Switchable Fluorescence of a Mechanical Stimulus-Responsive Au-P-S Complex. Molecules 2024, 29, 5736. [Google Scholar] [CrossRef] [PubMed]
  63. Cui, L.; Zhang, J.; Yan, S.; Yang, N.; Young, D.J.; Li, H.-X.; He, X.; Lu, Y.; Ren, Z.-G. A phosphorescent Au-P complex exhibiting ROS generation, enhanced emission in polymers and photodynamic inactivation of bacteria activities. J. Mol. Struc. 2025, 1337, 142254. [Google Scholar] [CrossRef]
  64. Pal, S.; Kathewad, N.; Pant, R.; Khan, S. Synthesis, Characterization, and Luminescence Studies of Gold(I) Complexes with PNP- and PNB-Based Ligand Systems. Inorg. Chem. 2015, 54, 10172–10183. [Google Scholar] [CrossRef]
  65. Kathewad, N.; Kumar, N.; Dasgupta, R.; Ghosh, M.; Pal, S.; Khan, S. The syntheses and photophysical properties of PNP-based Au(I) complexes with strong intramolecular Au⋯Au interactions. Dalton Trans. 2019, 48, 7274–7280. [Google Scholar] [CrossRef]
  66. Sathyanarayana, A.; Nakamura, S.-Y.; Hisano, K.; Tsutsumi, O.; Srinivas, K.; Prabusankar, G. Controlling the solid-state luminescence of gold(I) N-heterocyclic carbene complexes through changes in the structure of molecular aggregates. Sci. China Chem. 2018, 61, 957–965. [Google Scholar] [CrossRef]
  67. Wang, X.-Y.; Zhang, J.; Dong, Y.-B.; Zhang, Y.; Yin, J.; Liu, S.H. Different structures modulated mechanochromism and aggregation-induced emission in a series of Gold(I) complexes. Dye. Pigment. 2018, 156, 74–81. [Google Scholar] [CrossRef]
  68. Chen, Z.; Liu, G.; Pu, S.; Liu, S.H. Bipyridine-based aggregation-induced phosphorescent emission (AIPE)-active gold(I) complex with reversible phosphorescent mechanochromism and self-assembly characteristics. Dye. Pigment. 2018, 152, 54–59. [Google Scholar] [CrossRef]
  69. Lu, T.; Chen, F. Multiwfn: A multifunctional wavefunction analyzer. J. Comput. Chem. 2012, 33, 580–592. [Google Scholar] [CrossRef]
  70. Tang, W.-J.; Yang, H.; Peng, S.-K.; Xiao, Z.-M.; Huang, G.-Q.; Zheng, J.; Li, D. Multistimuli-responsive behavior of a phosphorescent Cu3pyrazolate3complex for luminescent logic gates and encrypted information transformation. Inorg. Chem. Front. 2023, 10, 2594–2606. [Google Scholar] [CrossRef]
  71. Zhang, J.-F.; Xin, G.; Fu, W.-F.; Xu, H.; Li, L. Interaction of free functional group with platinum(II) center in cyclometalated complexes: A structural and photophysical property investigation. Inorganica Chim. Acta 2010, 363, 338–345. [Google Scholar] [CrossRef]
  72. Sheldrick, G.M. SHELXTL-2016; Universität Göttingen: Göttingen, Germany, 2016. [Google Scholar]
  73. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Petersson, G.A.; Nakatsuji, H.; et al. Gaussian 16 Rev. C.01; Gaussian, Inc.: Wallingford, CT, USA, 2016. [Google Scholar]
Molecules 30 02011 sch001
Scheme 1. Synthesis of compound 1.
Scheme 1. Synthesis of compound 1.
Molecules 30 02011 sch001
Molecules 30 02011 g001
Figure 1. Crystal structure of 1·EtOH with 30% thermal ellipsoids. All H atoms, disordered F atoms, and the EtOH solvent molecule are omitted for clarity. Symmetry code for A: 1 − x, 1 − y, 1 − z.
Figure 1. Crystal structure of 1·EtOH with 30% thermal ellipsoids. All H atoms, disordered F atoms, and the EtOH solvent molecule are omitted for clarity. Symmetry code for A: 1 − x, 1 − y, 1 − z.
Molecules 30 02011 g001
Molecules 30 02011 g002
Figure 2. Excitation (dotted line) and emission (solid line) spectra of 1 in the solid state and in solution (1 mg/mL).
Figure 2. Excitation (dotted line) and emission (solid line) spectra of 1 in the solid state and in solution (1 mg/mL).
Molecules 30 02011 g002
Molecules 30 02011 g003
Figure 3. The orbital distributions of HOMOs and LUMOs (isovalue = 0.03) in compound 1.
Figure 3. The orbital distributions of HOMOs and LUMOs (isovalue = 0.03) in compound 1.
Molecules 30 02011 g003
Molecules 30 02011 g004
Figure 4. Comparisons of (a) emission spectra (excited at 354 nm), (b) photos under 365 nm LED irradiation, (c) CIE plot, (d) PXRD patterns of 1, in response to different pressures for 10 min (1—1 MPa, 1—2.5 MPa, 1—5 MPa, 1—10 MPa, 1—20 MPa), 1r (1—5 MPa after exposure to CH2Cl2 vapor), 1g (1 ground in a mortar), and 1gr (1g after exposure to CH2Cl2 vapor).
Figure 4. Comparisons of (a) emission spectra (excited at 354 nm), (b) photos under 365 nm LED irradiation, (c) CIE plot, (d) PXRD patterns of 1, in response to different pressures for 10 min (1—1 MPa, 1—2.5 MPa, 1—5 MPa, 1—10 MPa, 1—20 MPa), 1r (1—5 MPa after exposure to CH2Cl2 vapor), 1g (1 ground in a mortar), and 1gr (1g after exposure to CH2Cl2 vapor).
Molecules 30 02011 g004
Molecules 30 02011 g005
Figure 5. (a) Hydrogen bonds (dashed light-blue lines) between the [Au2(2-bdppmapy)2]2+ dication and the PF6− anions. All non-hydrogen-bonded H atoms are omitted for clarity; (b) C–H···π interactions (dashed yellow lines) between neighbouring [Au2(2-bdppmapy)2]2+ dications. All hydrogen atoms and PF6− anions are omitted for clarity. Atom colors: Au, light-yellow; P, magenta; N, blue; C, gray; F, green; H, white.
Figure 5. (a) Hydrogen bonds (dashed light-blue lines) between the [Au2(2-bdppmapy)2]2+ dication and the PF6− anions. All non-hydrogen-bonded H atoms are omitted for clarity; (b) C–H···π interactions (dashed yellow lines) between neighbouring [Au2(2-bdppmapy)2]2+ dications. All hydrogen atoms and PF6− anions are omitted for clarity. Atom colors: Au, light-yellow; P, magenta; N, blue; C, gray; F, green; H, white.
Molecules 30 02011 g005
Molecules 30 02011 g006
Figure 6. The Hirshfeld surface analysis of compound 1. Light-blue and yellow arrows directed to the hydrogen bonds and C–H···π interactions, respectively.
Figure 6. The Hirshfeld surface analysis of compound 1. Light-blue and yellow arrows directed to the hydrogen bonds and C–H···π interactions, respectively.
Molecules 30 02011 g006
Molecules 30 02011 g007
Figure 7. Comparison of the IR spectra of 1, 1—5 MPa, and 1r in the range 800–1600 cm−1.
Figure 7. Comparison of the IR spectra of 1, 1—5 MPa, and 1r in the range 800–1600 cm−1.
Molecules 30 02011 g007
Molecules 30 02011 g008
Figure 8. (left) Schematic plot of the encrypted information transfer experiment; (right) photos of the ‘secret writing paper’ under natural and UV (365 nm) light before/after writing ‘SCU’ and erasing with CH2Cl2 vapor.
Figure 8. (left) Schematic plot of the encrypted information transfer experiment; (right) photos of the ‘secret writing paper’ under natural and UV (365 nm) light before/after writing ‘SCU’ and erasing with CH2Cl2 vapor.
Molecules 30 02011 g008
Table 1. Hydrogen bond lengths (Å) and angles (°) in 1 (calculated by PLATON v1.18).
Table 1. Hydrogen bond lengths (Å) and angles (°) in 1 (calculated by PLATON v1.18).
D–H···AD–HH···AD···AD–H···A
C1–H1B···F30.982.423.35(2)157
C2–H2A···F6 i0.982.483.09(2)120
C6–H6···F4 ii0.942.433.21(2)141
C21–H21···F2 i0.942.513.34(2)147
Symmetry codes: (i) 0.5 − x, −0.5 + y, 1.5 − z; (ii) −x, 1 − y, 1 − z.
Table 2. C–H···π interaction distances (Å) and γ angles (°) in 1 (calculated by PLATON v1.18).
Table 2. C–H···π interaction distances (Å) and γ angles (°) in 1 (calculated by PLATON v1.18).
D–H···CgH···Cgγ
C9–H9···Cg1 i2.767.7
C17–H17···Cg1 ii2.8410.9
C22–H22···Cg2 iii2.9111.9
C23–H23···Cg3 iii2.868.7
Cg1: N2, C3–C7; Cg2: C8–C13; Cg3: C14–C19; Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 0.5 − x, 0.5 + y, 1.5 − z; (iii) 1.5 − x, −0.5 + y, 1.5 − z.
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Yang, N.; Chang, Y.; Wang, J.; Young, D.J.; Li, H.-X.; Lu, Y.; Ren, Z.-G. Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex. Molecules 2025, 30, 2011. https://doi.org/10.3390/molecules30092011

AMA Style

Yang N, Chang Y, Wang J, Young DJ, Li H-X, Lu Y, Ren Z-G. Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex. Molecules. 2025; 30(9):2011. https://doi.org/10.3390/molecules30092011

Chicago/Turabian Style

Yang, Ningwen, Yijia Chang, Jiangyue Wang, David James Young, Hong-Xi Li, Yuxin Lu, and Zhi-Gang Ren. 2025. "Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex" Molecules 30, no. 9: 2011. https://doi.org/10.3390/molecules30092011

APA Style

Yang, N., Chang, Y., Wang, J., Young, D. J., Li, H.-X., Lu, Y., & Ren, Z.-G. (2025). Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex. Molecules, 30(9), 2011. https://doi.org/10.3390/molecules30092011

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