期刊
INORGANIC CHEMISTRY
卷 56, 期 11, 页码 6438-6450出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.7b00510
关键词
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资金
- Regione Lombardia-Fondazione Cariplo joint SmartMatLab Project (Fondazione Cariplo Grant) [2013-1766]
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 beta-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 H-1 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.
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