Hexagonal Layered Materials Composed of [M2(O2CCF3)4] (M=Ru and Rh) Donors and TCNQ Acceptors

Abstract

π delocalization throughout the extended layers of two‐dimensional network polymers of the type [{M2(O2CCF3)4}2(TCNQ)⋅3 (C7H8)]∞, which consist of RuII,RuII and RhII,RhII complexes coordinated to TCNQ molecules, is evident from the available structural (see picture for Ru analogue) and spectroscopic data. TCNQ=7,7,8,8‐tetracyano‐p‐quinodimethane.

Impact of Metal-Ion Dependence on the Porous and Electronic Properties of TCNQ-Dianion-Based Porous Coordination Polymers

“…[31][32][33][34] In addition, TCNQ is suitable for forming high-dimensional coordination networks because of the coordination and structural diversities based on its multidentate nature and dimerization reaction. [35][36][37][38][39][40][41][42] The TCNQ in the frameworks acts as a good interaction site for guest adsorption and recognition, resulting in it showing unique sorption properties such as selective organic and gas sorption, 30 as well as guest-responsive color changes based on the chargetransfer (CT) interaction. 29 In contrast to the organic ligands, the metal ions are not considered to be the important component for the unique porous properties in these PCP systems.…”

Utilizing Perylene in New Organic Donor–Acceptor Materials: Highlighting the Synthesis, Structure and Physical Properties of Perylene-pDNB and Perylene-TCNP

“…For this family of acceptors, any spontaneous electron transfer from the donor to the acceptor is accompanied by a lengthening of the cyanide bond distances as electrons are donated into the group's antibonding p*-orbitals [44,45]. Upon comparing the cyanide bond distances for TCNP in its neutral form to those in 2, the mean cyanide bond distance in the former is 1.141(2) Å , while in the latter it was found to be 1.143(2) Å [46].…”

“…DM-DCNQI = 2,5-dimethyl-dicyanoquinonediimine) shift to lower frequency values upon acceptor reduction [44,45]. According to a literature report by Miller and coworkers, the vibrational frequency for the terminal cyanide within TCNP vibrates at a frequency of 2248 cm -1 [47].…”

[Cu3(dppm)3(μ 3-I)2][(0.5TCNQ)], a radical salt derived from a donor with a copper(I) trimer

“…The color of 1 is red, which is in accord with a TCNQ that is not neutral. The electronic spectral features of reduced TCNQ in the visible region typically give rise to green or red colors due to an intense -* transition, the exact energy of which is determined by the degree of charge transfer [10].…”