Electrochromic second-order NLO chromophores based on M-II (M = Ni, Pd, Pt) complexes with diselenolato-dithione (donor-acceptor) ligands

Davide Espa, Luca Pilia, Luciano Marchio, Maddalena Pizzotti, Neil Robertson, Francesca Tessore, M. Laura Mercuri, Angela Serpe, Paola Deplano

Research output: Contribution to journalArticlepeer-review

Abstract

The donor-acceptor type mixed-ligand complexes [M(Bz(2)pipdt)(dsit)]; dsit = 2-thioxo-1,3-dithiole-4,5-diselenolato (donor); Bz(2)pipdt = 1,4-dibenzyl-piperazine-2,3-dithione (acceptor); M(II) = Ni (1), Pd (2), and Pt (3) were prepared and characterized to investigate the variation of the properties by substituting selenium for sulfur in the donor ligand dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato of the corresponding known complexes. Both these classes of complexes exhibit large negative second-order polarizabilities, amongst the highest values determined so far for metal-complexes, and are potential candidates for redox switchability of the molecular first hyperpolarizability due to the bleaching/restoring of the solvatochromic peak for mono-reduction/oxidation. DFT and TD-DFT calculations on 1-3 allow one to correlate geometries and electronic structures and are in agreement with the observed minor changes following the substitution of selenium for sulfur atoms in the dichalcogenolato ligand. The observed differences can be ascribed to the increased size of the selenium atom leading to increased M-X distances and dipolar moments of the ground state, which are highest for the Pd-derivative in the triad.

Original languageEnglish
Pages (from-to)12106-12113
Number of pages8
JournalDalton Transactions
Volume41
Issue number39
DOIs
Publication statusPublished - 18 Sep 2012

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