Synthetic Exploration of Bis(phenolate) Aza-BODIPYs and Heavier Group 13 Chelates

A series of boron, aluminum, gallium, and indium chelates containing the underexplored bis(phenolate) aza-dipyrromethene (aza-DIPY) core were prepared. These compounds were found to possess near-infrared absorption and emission profiles in the 710 to 770 nm domain and exhibit quantum yield values up to 14%. X-ray diffraction analysis revealed that heavier group 13 bis(phenolate) aza-DIPY chelates possessed octahedral geometries with either THF or pyridine groups occupying the axial positions as opposed to the tetrahedral geometry of the boron chelate.


Introduction
Since its resurgence nearly two decades ago, the aza-dipyrromethene (aza-DIPY) core (A, Figure 1) has received significant attention due to its intense absorbing and emitting profile in the near-infrared (NIR) region which makes them exciting candidates for application in both the physical and biological sciences [1][2][3][4]. From the perspective of effectively modulating these profiles, boron difluoride chelates of the aza-DIPY core (aza-BODIPYs, (B) represent the majority of literature examples as numerous strategies are known to push absorption and emission maxima beyond 800 nm [5][6][7][8][9][10].

Introduction
Since its resurgence nearly two decades ago, the aza-dipyrromethene (aza-DIPY) core (A, Figure 1) has received significant attention due to its intense absorbing and emitting profile in the near-infrared (NIR) region which makes them exciting candidates for application in both the physical and biological sciences [1][2][3][4]. From the perspective of effectively modulating these profiles, boron difluoride chelates of the aza-DIPY core (aza-BODIPYs, (B) represent the majority of literature examples as numerous strategies are known to push absorption and emission maxima beyond 800 nm [5][6][7][8][9][10].  In conjunction with our prior work functionalizing aza-BODIPYs through the direct incorporation of nitro groups [11], we became interested with the bis(phenolate) aza-DIPY core structure (C), having ortho-functionalized phenolic groups present on the proximal rings. Motivation for this core structure stemmed from the previous work done by Burgess and others which demonstrated that bis(phenolate) aza-BODIPYs can achieve absorption and emission maxima upwards of 780 nm [12][13][14][15][16][17][18]. Additionally, very recent work by Sauvé and coworkers detailed that the addition of phenylacetylene groups on the 2-and 6-positions of the bis(phenolate) aza-BODIPY core can further shift absorption and emission maxima past 820 nm [19].
The structurally related bis(phenolate) dipyrromethene core (D), whose boron chelates were also originally reported by Burgess and coworkers [20], represents a secondary source of inspiration as numerous elements beyond boron have also been chelated to afford a diverse array of compounds with interesting structural and photophysical properties. For example, Nabeshima and coworkers explored the insertion of heavier Group 13 centers (Al, Ga, In, E) and found that such complexes were able to serve as efficient luminescent sensors to both alkaline earth and transition metals [21][22][23]. Further work by their group also considered the insertion of Group 14 and 15 centers which yielded chelates that incorporate both bent and linear oxygen bonds and serve as zwitterionic NIR pH sensors [24][25][26][27]. Significant work on inserting transition metal centers into the bis(phenolate) DIPY core has also been performed. For example, Nozaki and coworkers explored Group 4 and heavier Group 14 (Ti, Zr, Ge, Sn, F) DIPY chelates as catalysts for the copolymerization of epoxides with carbon dioxide [28]. Work by Thomas and others have also demonstrated that DIPY chelates containing Mn can serve as catalysts for olefin epoxidations [29][30][31]. Furthermore, numerous reports have indicated that both mid-and late-transition metal DIPY chelates can exhibit both innocent and non-innocent redox properties [32][33][34][35]. Indeed, a recent 2019 report by Kadish and coworkers [36] directly suggested that such behavior with bis(phenolate) DIPYs may very well serve as an analogy for the well-known corrole macrocycle which has received significant attention in its own right over the past three decades. This analogy is also the subject of a very recent review by Paolesse and coworkers [37].
To the best of our knowledge, no chelates outside of boron that contain the bis(phenolate) aza-DIPY core structure are currently known to the literature. Given the likely structural properties that such chelates will share with their DIPY congeners in addition to their expected NIR traits, further research is of clear interest. Here, we disclose the synthesis of a series of aza-BODIPY (1a-b), aza-ALDIPY (2a-b), aza-GADIPY (3a-b), and aza-INDIPY (4a-b) complexes. This series of compounds lays the groundwork for a thorough investigation of this comparatively underexplored class of molecules and validates their expected structural and spectral properties. In addition to their 1 H, 11 B, 13 C and HRMS data, we also report the X-ray structures of 1a, 2a-b, 3a-b, and 4a-b which unambiguously confirm their structural identities. Finally, the computational and photophysical properties of 1a-b, 2a-b, 3a-b, and 4a-b are discussed and compared.

Crystallography
Single crystals of bis(phenolate) aza-BODIPY 1a were obtained through the slow vapor diffusion of a THF solution of 1a with n-pentane. Analysis of the diffraction data unambiguously confirms the structural identity of 1a and its expected tetrahedral boron center ( Figure 2). To accommodate this coordination geometry, both phenolic rings exhibit significant flexing as demonstrated by torsion angles of −22.23(9)° and −24.41(4)° along C2-C1-C9-C14 and C6-C5-C15-C20, respectively. All reactions were monitored through observation of a characteristic upfield shift of the pyrrolic 1 H signal correlating to the 2-and 6-positions of the bis(phenolate) aza-DIPY core. Additionally, boron chelations were followed through the expected appearance of a 11 B singlet between −3.5 and −2.5 ppm. For aluminum, gallium, and indium chelations, we observed the appearance of pyridine signals in an approximate 2:1 ratio with respect to the bis(phenolate) aza-DIPY core, implying the inclusion of two axially bound pyridine units to the metal center, completing their expected octahedral geometries.

Crystallography
Single crystals of bis(phenolate) aza-BODIPY 1a were obtained through the slow vapor diffusion of a THF solution of 1a with n-pentane. Analysis of the diffraction data unambiguously confirms the structural identity of 1a and its expected tetrahedral boron center ( Figure 2). To accommodate this coordination geometry, both phenolic rings exhibit significant flexing as demonstrated by torsion angles of −22.23(9) • and −24.41(4) • along C2-C1-C9-C14 and C6-C5-C15-C20, respectively. Single crystals of bis(phenolate) aza-ALDIPY 2a were obtained through layering nhexane in a 1:1 pyridine:toluene solution followed by slow evaporation. As seen in Figure  3, two pyridine groups are bound axially to the Al center, giving a nearly linear angle of 176.55(7)° along the N4-Al1-N5 axis. The Al center also fits within the plane of the bis(phenolate) aza-DIPY core and we observe the phenolic rings puckering slightly inwards, resulting in an interplanar angle of 3.31(8)°. These structural trends are similarly found with the diffraction data of 2b, 3a-b, and 4a-b (see the Supporting Information for full details). Interestingly, when THF was used as a coordinating solvent instead of pyridine, single crystals of bis(phenolate) aza-INDIPY 4a' were obtained through layering ndecane over a saturated THF solution. As seen in Figure 4, 4a' incorporates two identical octahedral aza-INDIPY cores that are dimerized together forming a central four-membered ring that contains an In2O2 moiety (In1-O2: 2.141 Å ; In1-O2': 2.224 Å ). The axially bound THF groups (omitted for clarity, see Supporting Information) are also moderately bent out of linearity as evidenced from the 163.81(12)° angle along the O3-In1-O2' axis. There is also significant twisting (17.44(3)°) between the axially bound phenolic group and the aza-DIPY core to accommodate dimerization which also explains the discrete In-O bond lengths.  Single crystals of bis(phenolate) aza-ALDIPY 2a were obtained through layering n-hexane in a 1:1 pyridine:toluene solution followed by slow evaporation. As seen in Figure 3, two pyridine groups are bound axially to the Al center, giving a nearly linear angle of 176.55(7) • along the N4-Al1-N5 axis. The Al center also fits within the plane of the bis(phenolate) aza-DIPY core and we observe the phenolic rings puckering slightly inwards, resulting in an interplanar angle of 3.31(8) • . These structural trends are similarly found with the diffraction data of 2b, 3a-b, and 4a-b (see the Supporting Information for full details). Interestingly, when THF was used as a coordinating solvent instead of pyridine, single crystals of bis(phenolate) aza-INDIPY 4a' were obtained through layering n-decane over a saturated THF solution. As seen in Figure 4, 4a' incorporates two identical octahedral aza-INDIPY cores that are dimerized together forming a central four-membered ring that contains an In 2 O 2 moiety (In1-O2: 2.141 Å; In1-O2': 2.224 Å). The axially bound THF groups (omitted for clarity, see Supporting Information) are also moderately bent out of linearity as evidenced from the 163.81 (12) • angle along the O3-In1-O2' axis. There is also significant twisting (17.44(3) • ) between the axially bound phenolic group and the aza-DIPY core to accommodate dimerization which also explains the discrete In-O bond lengths. Single crystals of bis(phenolate) aza-ALDIPY 2a were obtained through layering nhexane in a 1:1 pyridine:toluene solution followed by slow evaporation. As seen in Figure  3, two pyridine groups are bound axially to the Al center, giving a nearly linear angle of 176.55(7)° along the N4-Al1-N5 axis. The Al center also fits within the plane of the bis(phenolate) aza-DIPY core and we observe the phenolic rings puckering slightly inwards, resulting in an interplanar angle of 3.31(8)°. These structural trends are similarly found with the diffraction data of 2b, 3a-b, and 4a-b (see the Supporting Information for full details). Interestingly, when THF was used as a coordinating solvent instead of pyridine, single crystals of bis(phenolate) aza-INDIPY 4a' were obtained through layering ndecane over a saturated THF solution. As seen in Figure 4, 4a' incorporates two identical octahedral aza-INDIPY cores that are dimerized together forming a central four-membered ring that contains an In2O2 moiety (In1-O2: 2.141 Å ; In1-O2': 2.224 Å ). The axially bound THF groups (omitted for clarity, see Supporting Information) are also moderately bent out of linearity as evidenced from the 163.81(12)° angle along the O3-In1-O2' axis. There is also significant twisting (17.44(3)°) between the axially bound phenolic group and the aza-DIPY core to accommodate dimerization which also explains the discrete In-O bond lengths.   Ellipsoids are drawn at the 40% probability level. Axial THF groups and hydrogen atoms have been removed for clarity.

Computational Measurements
To better understand the photophysical properties of 1a-b, 2a-b, 3a-b¸and 4a-b, density functional theory (DFT) calculations were performed [38,39]. All data are given in Table 1 with the frontier molecular orbitals of 1a, 2a, 3a, and 4a displayed in Figure 5 (see the Supporting Information for full details). Using the experimentally determined crystal structure of 2a as a reference, the computed ground state geometries were found to be in excellent agreement using the B3LYP functional with Dunning's jul-cc-pVDZ basis set [40]. The jul-cc-pVDZ basis set was selected due to its good performance in a variety of systems [41] and in our prior studies, we found it gave the best balance of accuracy and computational cost for functionalized DIPYs [11]. With the optimized structures in hand, TD-DFT calculations using B3LYP/jul-cc- pVDZ for 1a-b, 2a-b, and 3a-b with MeOH as the implicit solvent [42,43] were performed; for 4a-b, B3LYP/LanL2DZ was used for both geometry optimization and TD-DFT calculations to accommodate the In nuclei [44,45]. Overall, our computations generated theoretical λabs values that closely matched their experimental values with deviations below 5%; the sole exception to this was bis(phenolate) aza-BODIPY 1a which exhibited a deviation of 9.1%.

Computational Measurements
To better understand the photophysical properties of 1a-b, 2a-b, 3a-b¸and 4a-b, density functional theory (DFT) calculations were performed [38,39]. All data are given in Table 1 with the frontier molecular orbitals of 1a, 2a, 3a, and 4a displayed in Figure 5 (see the Supporting Information for full details). Using the experimentally determined crystal structure of 2a as a reference, the computed ground state geometries were found to be in excellent agreement using the B3LYP functional with Dunning's jul-cc-pVDZ basis set [40]. The jul-cc-pVDZ basis set was selected due to its good performance in a variety of systems [41] and in our prior studies, we found it gave the best balance of accuracy and computational cost for functionalized DIPYs [11]. With the optimized structures in hand, TD-DFT calculations using B3LYP/jul-cc- pVDZ for 1a-b, 2a-b, and 3a-b with MeOH as the implicit solvent [42,43] were performed; for 4a-b, B3LYP/LanL2DZ was used for both geometry optimization and TD-DFT calculations to accommodate the In nuclei [44,45]. Overall, our computations generated theoretical λ abs values that closely matched their experimental values with deviations below 5%; the sole exception to this was bis(phenolate) aza-BODIPY 1a which exhibited a deviation of 9.1%.
As seen in Figure 5, both methyl and methoxy-functionalized bis(phenolate) aza-MDIPYs possess little orbital density on the distal arenes which suggests that such functionalization bears little influence. Instead, the majority of HOMO and LUMO density resides on the aza-DIPY core, resulting in the expected π-π* transitions. Furthermore, little to no orbital density was found on the metal centers which agrees with numerous aza-DIPY studies performed previously [12][13][14][15][16][17][18]46,47]. Perhaps the greatest difference between the frontier molecular orbital plots of these compounds involves the LUMO+1 orbital as 1a-b has orbital density spread throughout the proximal rings and aza-DIPY core while 2a-b, 3a-b, and 4a-b have orbital density exclusively on the axially bound pyridines. These structures were also visualized in the DIPY plane, with the images included in the SI. As seen in Figure 5, both methyl and methoxy-functionalized bis(phenolate) aza-MDIPYs possess little orbital density on the distal arenes which suggests that such functionalization bears little influence. Instead, the majority of HOMO and LUMO density resides on the aza-DIPY core, resulting in the expected π-π* transitions. Furthermore, little to no orbital density was found on the metal centers which agrees with numerous aza-DIPY studies performed previously [12][13][14][15][16][17][18]46,47]. Perhaps the greatest difference between the frontier molecular orbital plots of these compounds involves the LUMO+1 orbital as 1a-b has orbital density spread throughout the proximal rings and aza-DIPY core while 2a-b¸3a-b, and 4a-b have orbital density exclusively on the axially bound pyridines. These structures were also visualized in the DIPY plane, with the images included in the SI.  -DIPYs 1a-b, 2a-b, 3a-b, and  4a- 1a-b, 2a-b, and 3a-b with MeOH as implicit solvent; B3LYP/LanL2DZ was used for 4a-b with MeOH as implicit solvent.

Photophysical Properties 2.4.1. Electronic Absorption Spectra
The absorption spectra for 1a-b, 2a-b, 3a-b and 4a-b in DMSO are shown in Figure 6 and listed in Table 1. As expected with most aza-BODIPYs, all compounds exhibited intense absorption maxima between 715-735 nm with extinction coefficients between 30,000 and 52,000 M −1 cm −1 . Also present are smaller absorption maxima located at the 650 nm, 450 nm, and 325 nm ranges. Interestingly, 1a-b exhibit bathochromically shifted absorptions in the 525 nm range as compared to 2a-b, 3a-b, and 4a-b which give them a purple hue compared to the green color that the remaining complexes possess. As predicted by the frontier molecular orbital plots mentioned above, para-functionalization on the distal positions of the bis(phenolate) aza-DIPY core had little effect on the absorption maxima which was similarly observed by Burgess and coworkers regarding aza-BODIPYs [18]. The general trend was found to be B > Ga > Al > In with bis(phenolate) aza-BODIPYs 1a-b exhibiting the most bathochromically shifted absorption spectra which fits well with prior observations found by Nabeshima and co-workers [23].
a Spectra were obtained in MeOH at 10 μM. Wavelengths are in nm. b Optical HOMO/LUMO gap was determined at λabs. c λabs was used as the excitation wavelength for λem. Stokes shifts (SS) are measured in both nm and cm −1 . Quantum yields are measured using an internal integrating sphere in ambient air at room temperature and are reported in %. d Calculations were performed using B3LYP/jul-cc- pVDZ for 1a-b, 2a-b, and 3a-b with MeOH as implicit solvent; B3LYP/LanL2DZ was used for 4a-b with MeOH as implicit solvent.

Electronic Absorption Spectra
The absorption spectra for 1a-b, 2a-b, 3a-b and 4a-b in DMSO are shown in Figure 6 and listed in Table 1. As expected with most aza-BODIPYs, all compounds exhibited intense absorption maxima between 715-735 nm with extinction coefficients between 30,000 and 52,000 M −1 cm −1 . Also present are smaller absorption maxima located at the 650 nm, 450 nm, and 325 nm ranges. Interestingly, 1a-b exhibit bathochromically shifted absorptions in the 525 nm range as compared to 2a-b, 3a-b, and 4a-b which give them a purple hue compared to the green color that the remaining complexes possess. As predicted by the frontier molecular orbital plots mentioned above, para-functionalization on the distal positions of the bis(phenolate) aza-DIPY core had little effect on the absorption maxima which was similarly observed by Burgess and coworkers regarding aza-BODIPYs [18]. The general trend was found to be B > Ga > Al > In with bis(phenolate) aza-BODIPYs 1ab exhibiting the most bathochromically shifted absorption spectra which fits well with prior observations found by Nabeshima and co-workers [23].  1a-b, 2a-b, 3a-b, and 4a-b in DMSO. All spectra are recorded at a concentration of 10 μM.

Electronic Emission Spectra
The emission spectra for 1a-b, 2a-b, 3a-b and 4a-b in DMSO are shown in Figure 7 and listed in Table 1. Unlike the absorption data, the general emission trend stands at Ga > Al > B > In with bis(phenolate) aza-GADIPYs 2a-b exhibiting the most bathochromically shifted spectra. As found with the observations originally made by both Nabeshima and Burgess [18,23], methyl functionalized derivatives exhibited bathochromically shifted emission maxima when compared to their methoxy functionalized derivatives. With respect to Stokes shifts, the general trend stands at Ga > In > Al > B; this observation is reasoned to be due to the difference between the octahedral geometry of 2a-b, 3a-b, and 4ab compared to the tetrahedral geometry of 1a-b. Quantum yields for 1a-b, 2a-b, 3a-b, and 4a-b were also measured in MeOH using an internal integrating sphere and their values

Electronic Emission Spectra
The emission spectra for 1a-b, 2a-b, 3a-b and 4a-b in DMSO are shown in Figure 7 and listed in Table 1. Unlike the absorption data, the general emission trend stands at Ga > Al > B > In with bis(phenolate) aza-GADIPYs 2a-b exhibiting the most bathochromically shifted spectra. As found with the observations originally made by both Nabeshima and Burgess [18,23], methyl functionalized derivatives exhibited bathochromically shifted emission maxima when compared to their methoxy functionalized derivatives. With respect to Stokes shifts, the general trend stands at Ga > In > Al > B; this observation is reasoned to be due to the difference between the octahedral geometry of 2a-b, 3a-b, and 4a-b compared  to the tetrahedral geometry of 1a-b. Quantum yields for 1a-b, 2a-b, 3a-b, and 4a-b were also measured in MeOH using an internal integrating sphere and their values are given in Table 1. It was found that quantum yields increased from 1a-b to 2a-b but then decreased as a function of increasing metal size. are given in Table 1. It was found that quantum yields increased from 1a-b to 2a-b but then decreased as a function of increasing metal size.

General Considerations
Unless otherwise noted, solvents and reagents were purchased from either Thermo Fisher or Sigma Aldrich and used as received. Flash chromatography was performed using P60 silica purchased from SiliCycle. THF was distilled from sodium/benzophenone under a nitrogen atmosphere. Bis(phenolate) aza-BODIPY 7b and their precursors, 5b and 6b, were synthesized by their previously reported methods [18,23].
NMR spectra were recorded using a JEOL JMN-ECSZ400R 400 MHz ( 1 H: 399.78 MHz; 13 C: 100.52 MHz) spectrometer at room temperature. Chemical shifts (δ) are expressed in ppm relative to the residual chloroform ( 1 H: 7.27 ppm; 13 C: 77.2 ppm) or DMSOd 6 ( 1 H: 2.50 ppm; 13 C: 39.5 ppm) in solution. Coupling constants are expressed in hertz. UV-Visible spectra were recorded on a Cary 100 UV-Vis spectrometer. Fluorescence spectra were recorded on a PTI HORIBA QM-40 spectrofluorometer and quantum yields were obtained using a KSPHERE petite integrating sphere. Single crystal XRD measurements were collected from a Bruker Smart Apex II CCD diffractometer using graphite-monochromated Mo-K (λα = 0.71073 Å ) radiation. Molecular crystal structure images were processed through CrystalMaker. HRMS-ESI measurements were taken on an Agilent 6530 high resolution quadrupole time of flight spectrometer (QTOF) utilizing an Agilent 1100 liquid chromatography system with model G1212A binary pump and G1367 autosampler. Samples were introduced via direct injection rather than isolating species with column chromatography to monitor changing levels of starting material as well as any potential side reactions which were ionized using a Dual Agilent Jet Stream G1958-66268 electrospray ionization source. Immediately prior to sample introduction, the QTOF was calibrated in the 50-1700 mass range for the 4 GHz high resolution mode. A mobile phase of HPLC acetone was utilized to reduce instrument noise related to the solvent and to ensure the analyte would stay in solution until ionized. Acetone was utilized as a needle wash to reduce contamination of samples. Samples were analyzed in the positive mode with a dragging gas temperature of 300 °C, a drying gas flow rate of 8 L/min, a nebulizer pressure of 35 psi, a sheath gas temperature of 350 °C, a sheath gas flow rate of 11 L/min, and a capillary voltage of 3500 V.

General Considerations
Unless otherwise noted, solvents and reagents were purchased from either Thermo Fisher or Sigma Aldrich and used as received. Flash chromatography was performed using P60 silica purchased from SiliCycle. THF was distilled from sodium/benzophenone under a nitrogen atmosphere. Bis(phenolate) aza-BODIPY 7b and their precursors, 5b and 6b, were synthesized by their previously reported methods [18,23].
NMR spectra were recorded using a JEOL JMN-ECSZ400R 400 MHz ( 1 H: 399.78 MHz; 13 C: 100.52 MHz) spectrometer at room temperature. Chemical shifts (δ) are expressed in ppm relative to the residual chloroform ( 1 H: 7.27 ppm; 13 C: 77.2 ppm) or DMSO-d 6 ( 1 H: 2.50 ppm; 13 C: 39.5 ppm) in solution. Coupling constants are expressed in hertz. UV-Visible spectra were recorded on a Cary 100 UV-Vis spectrometer. Fluorescence spectra were recorded on a PTI HORIBA QM-40 spectrofluorometer and quantum yields were obtained using a KSPHERE petite integrating sphere. Single crystal XRD measurements were collected from a Bruker Smart Apex II CCD diffractometer using graphite-monochromated Mo-K (λ α = 0.71073 Å) radiation. Molecular crystal structure images were processed through CrystalMaker. HRMS-ESI measurements were taken on an Agilent 6530 high resolution quadrupole time of flight spectrometer (QTOF) utilizing an Agilent 1100 liquid chromatography system with model G1212A binary pump and G1367 autosampler. Samples were introduced via direct injection rather than isolating species with column chromatography to monitor changing levels of starting material as well as any potential side reactions which were ionized using a Dual Agilent Jet Stream G1958-66268 electrospray ionization source. Immediately prior to sample introduction, the QTOF was calibrated in the 50-1700 mass range for the 4 GHz high resolution mode. A mobile phase of HPLC acetone was utilized to reduce instrument noise related to the solvent and to ensure the analyte would stay in solution until ionized. Acetone was utilized as a needle wash to reduce contamination of samples. Samples were analyzed in the positive mode with a dragging gas temperature of 300 • C, a drying gas flow rate of 8 L/min, a nebulizer pressure of 35 psi, a sheath gas temperature of 350 • C, a sheath gas flow rate of 11 L/min, and a capillary voltage of 3500 V.

Bis(phenolate) Aza-DIPY 7a
1,4-Product 6a (5.00 g, 16.7 mmol) and ammonium acetate (40.0 g, 519 mmol) were dissolved in 1-butanol (75 mL). The reaction mixture was heated to reflux and allowed to stir overnight. Upon cooling to room temperature, the resulting precipitate was collected over filter paper, washed with H 2 O (200 mL) and EtOH (200 mL), and the solid was allowed to dry in the oven at 85 • C to obtain 7a (1.57 g, 37%) as a brown iridescent solid. 1

Bis(phenolate) Aza-DIPY 7b
1,4-Product 6b (5.00 g, 15.9 mmol) and ammonium acetate (40.0 g, 519 mmol) were dissolved in 1-butanol (75 mL). The reaction mixture was heated to reflux and allowed to stir overnight. Upon cooling to room temperature, the resulting precipitate was collected over filter paper, washed with H 2 O (200 mL) and EtOH (200 mL), and the solid was allowed to dry in the oven at 85 • C to obtain 7b (1.60 g, 37%) as a brown iridescent solid. The compound's 1 H NMR spectrum matched the known spectrum [18].

Bis(phenolate) Aza-ALDIPY 2a
To a solution of pyridine (15 mL), bis(phenolate) aza-DIPY 7a (0.150 g, 0.294 mmol) and Al(acac) 3 (0.146 g, 0.441 mmol) were added and the mixture was heated to reflux overnight. Upon cooling to room temperature, hexanes (30 mL) was added to the mixture and cooled to 0 • C. Once cold, the resulting precipitate was collected over filter paper, washed with additional hexanes (30 mL) and evaporated from dryness to afford 2a (0.212 g, 72%) as a dark green solid. 1

Bis(phenolate) Aza-ALDIPY 2b
To a solution of pyridine (15 mL), bis(phenolate) aza-DIPY 7b (0.150 g, 0.277 mmol) and Al(acac) 3 (0.124 g, 0.415 mmol) were added and the mixture was heated to reflux overnight. Upon cooling to room temperature, hexanes (30 mL) was added to the mixture and cooled to 0 • C. Once cold, the resulting precipitate was collected over filter paper, washed with additional hexanes (30 mL) and evaporated from dryness to afford 1b (0.134 g, 67%) as a dark green solid. 1

Bis(phenolate) Aza-GADIPY 3a
To a solution of pyridine (15 mL), bis(phenolate) aza-DIPY 7a (0.150 g, 0.294 mmol) and Ga(acac) 3 (0.162 g, 0.441 mmol) were added and the mixture was heated to reflux overnight. Upon cooling to room temperature, hexanes (30 mL) was added to the mixture and cooled to 0 • C. Once cold, the resulting precipitate was collected over filter paper, washed with additional hexanes (30 mL) and evaporated from dryness to afford 3a (0.156 g, 72%) as a dark green solid. 1