(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

Abstract

The 3:2 Charge Transfer (CT) co-crystal (Perylene)3(TCNQF1)2 is grown by the Physical Vapor Transport (PVT) method, and characterized structurally and spectroscopically. Infrared analysis of the charge sensitive modes reveals a low degree of charge transfer (less than 0.1) between donor and acceptor molecules. The crystal is isostructural to the other 3:2 CT crystals formed by Perylene with TCNQF2 and TCNQF4, whereas such stoichiometry and packing is not known for the CT crystals with non-fluorinated TCNQ. The analysis of the isostructural family of 3:2 Perylene–TCNQFx (x = 1,2,4) co-crystal put in evidence the role of weak F…HC bonding in stabilizing this type of structure

The Stoichiometry of TCNQ-Based Organic Charge-Transfer Cocrystals

“…For example, in the perylene-TCNQ system, the DCT increases from 0.01 to 0.23 attributed to the increase in the number of perylene molecules from 1 to 3 in the unit cell [37]. However, in perylene-F 1 TCNQ, perylene-F 2 TCNQ, and perylene-F 4 TCNQ systems, the ratio between organic donors and acceptors is not an integer, which leads to nearly the same DCT [66,80]. For the 1:1 stoichiometry CTCs, the DCT increases dramatically with the increment of the number of F atoms.…”

“…In recent reports, the donor and acceptor can also form the 3:2 stoichiometry. There are two chains, and one chain adopts -D-A-D-A-stacking while another one takes -D-A-D-D-A-D-stacking (Figure 8f) [66]. It can be regarded as a mixed-stacking.…”

“…In general, the mixed stacking system exhibits a lower conductivity, while the segregated stack normally generates a higher conductivity. (f) is reproduced with permission from [66].…”

“…The red and blue rectangles represent the donor and acceptor constituents, respectively; (b) Crystal packing of the tetracene-F4TCNQ along the (100) direction; (c) Crystal packing of the TTF-TCNQ; (d) Crystal packing of the (perylene)2-(TCNQ)1; (e) Crystal packing of the (perylene)3-(TCNQ)1; (f) Crystal packing of the (perylene)3-(F4TCNQ)2. (a) is reproduced with permission from [2]; (b) is reproduced with permission from[42]; (c) is reproduced with permission from[6]; (d,e) are reproduced with permission from[37]; (f) is reproduced with permission from[66].…”

Synthesis of Low-Cost, Bio-Based Novel Adsorbent Material Using Charge-Transfer Interaction for Water Treatment from Several Pollutants: Waste to Worth

“…Researchers found that the resulting products via the CT interactions possess unique chemical, biological, and physical properties. The CT complexations are significantly beneficial to non-academic fields (pharmacology, material science, engineering, technology, and medicine) in addition to academia (chemistry, physics, biology, and biochemistry) [12][13][14][15][16][17][18][19][20][21][22][23][24].…”