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Impact of the Subunit Arrangement on the Nonlinear Absorption Properties of Organometallic Complexes with Ruthenium(II) σ-Acetylide and Benzothiadiazole as Building Units §

1
Department of Chemistry, Università degli Studi di Milano, UdR dell’INSTM, Via Golgi 19, 20133 Milano, Italy
2
Inorganic Functional Materials Research Institute (IFMRI), National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan
*
Author to whom correspondence should be addressed.
§
This paper is dedicated to Prof. Renato Ugo, on the occasion of his 80th birthday.
Inorganics 2019, 7(5), 67; https://doi.org/10.3390/inorganics7050067
Received: 29 April 2019 / Revised: 21 May 2019 / Accepted: 22 May 2019 / Published: 24 May 2019
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
In this paper, the nonlinear absorption properties of two complexes consisting of Ru(C≡CPh)(C≡C)(dppe)2 (dppe = Ph2PCH2CH2PPh2) as electron donor (D) and 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole as electron acceptor (A) units in two different arrangement, i.e., A–D–A and D–A–D, are presented. They were measured in solution by the femtosecond open-aperture Z-scan method. The complexes show moderate two-photon absorption cross-sections σ(2) of several hundred to one thousand GM (here 1 GM = 10−50 cm4 s molecule−1 photon−1). Although they are formed by the same building units, it was found that the two-photon absorption values of the D–A–D arrangement are six times higher than that of the A–D–A one. This difference can be explained by the number of metal cores (one or two ruthenium centers), the geometrical configurations of the complexes (more or less planar), and the resonance enhancement by lowering the intermediate state. View Full-Text
Keywords: third-order nonlinearity; two-photon absorption; Ru complex; benzothiadiazole; Z-scan third-order nonlinearity; two-photon absorption; Ru complex; benzothiadiazole; Z-scan
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MDPI and ACS Style

Garoni, E.; Colombo, A.; Kamada, K.; Dragonetti, C.; Roberto, D. Impact of the Subunit Arrangement on the Nonlinear Absorption Properties of Organometallic Complexes with Ruthenium(II) σ-Acetylide and Benzothiadiazole as Building Units §. Inorganics 2019, 7, 67.

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