Intriguing Influence of −COOH-Driven Intermolecular Aggregation and Acid-Base Interactions with N,N-Dimethylformamide on the Second-Order Nonlinear-Optical Response of 5,15 Push-Pull Diarylzinc(II) Porphyrinates

Orbelli Biroli, Alessio, Tessore, Francesca, Righetto, Stefania, Forni, Alessandra, Macchioni, Alceo, Rocchigiani, Luca, Pizzotti, Maddalena and Di Carlo, Gabriele (2017) Intriguing Influence of −COOH-Driven Intermolecular Aggregation and Acid-Base Interactions with N,N-Dimethylformamide on the Second-Order Nonlinear-Optical Response of 5,15 Push-Pull Diarylzinc(II) Porphyrinates. Inorganic Chemistry, 56 (11). pp. 6438-6450. ISSN 0020-1669

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Abstract

A series of 5,15 push–pull meso-diarylzinc(II) porphyrinates, carrying one or two −COOH or −COOCH3 acceptor groups and a −OCH3 or a −N(CH3)2 donor group, show in N,N-dimethylformamide and CHCl3 solutions a negative and solvent-dependent second-order nonlinear-optical (NLO) response measured by the electric-field-induced second-harmonic generation (EFISH) technique, different from the structurally related zinc(II) porphyrinate carrying a −N(CH3)2 donor group and a −NO2 acceptor group, where a still solvent-dependent but positive EFISH second-order response was previously reported. Moreover, when a −N(CH3)2 donor group and a −COOH acceptor group are part of a sterically hindered 2,12 push–pull β-pyrrolic-substituted tetraarylzinc(II) porphyrinate, the EFISH response is positive and solvent-independent. In order to rationalize these rather intriguing series of observations, EFISH measurements have been integrated by electronic absorption and IR spectroscopic investigations and by density functional theory (DFT) and coupled-perturbed DFT theoretical and 1H pulsed-gradient spin-echo NMR investigations, which prompt that the significant concentration effects and the strong influence of the solvent nature on the NLO response are originated by a complex whole of different aggregation processes induced by the −COOH group.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 09 Jul 2019 13:22
Last Modified: 18 Sep 2020 00:22
URI: https://ueaeprints.uea.ac.uk/id/eprint/71689
DOI: 10.1021/acs.inorgchem.7b00510

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