Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag^I Coordination Network

Abstract

A new 3D Ag(I)-based coordination network, [Ag2(pz)(bdc)·H2O]n (1; pz = pyrazine and H2bdc = benzene-1,3-dicarboxylic acid), was constructed by one-pot assembly and structurally established by single-crystal X-ray diffraction at different temperatures. Upon cooling from 298 to 93 K, 1 undergo an interesting single-crystal to single-crystal phase transition from orthorhombic Ibca (Z = 16) to Pccn (Z = 32) at around 148 K. Both phases show a rare 2-fold-interpenetrated 4-connected lvt network but incorporate different [Ag2(COO)2] dimeric secondary building units. It is worth mentioning that complex 1 shows red- and blue-shifted luminescences in the 290-170 and 140-80 K temperature ranges, respectively. The variable-temperature single-crystal X-ray crystallographic studies suggest that the argentophilic interactions and rigidity of the structure dominated the luminescence chromism trends at the respective temperature ranges. Upon being mechanically ground, 1 exhibits a slight mechanoluminescence red shift from 589 to 604 nm at 298 K.

Construction of Crystalline One‐Dimensional Infinite Argentophilic Silver Alkynyl Assemblies and their Luminescence Properties

“…[2a], Interestingly, compound 2 and 3 display a dual‐emissive characteristic at 83 K with shoulder peak both at about 616 nm, which may result from the separation of the LMCT and MC origin. [11a], Compound 1 is non‐emissive even at 77 K. This may be due to the lack of aryl group in its ligands, compared with compound 2 – 4 (aryl alkyne or aryl acid). Since the aryl group π systems may involve in the LMCT process related to the excitation state for emission, and the rigidity of aryl group contributes to reduce the nonradiative relaxation pathways.…”

“…Although a number of silver acetylides 1‐D structures are known, the photophysical properties of them are seldom investigated . As a continuous work of exploring structure well‐defined silver cluster‐base luminescent material,[9a], herein, we report the syntheses, structures and luminescence properties of four one‐dimensional (1‐D) silver alkynyl assemblies, namely, [Ag 11 ( t BuC≡C) 7 (CH 3 COO) 4 ] n ( 1 ), [Ag 21 ( t BuC≡C) 11 (PhCOO) 10 ] n ( 2 ), [Ag 16 ( m ‐F‐PhC≡C) 12 (CF 3 COO) 4 (CH 3 CN) 4 ] n ( 3 ) and [Cl@Ag 14 (PhC≡C) 10 (CF 3 SO 3 ) 3 ] n ( 4 ).…”

Solvent-mediated structural transformations of copper(II) coordination polymers induced by different short-chain alcohols

“…In addition, the flexibility of CPs also provided an opportunity to modify their bulk physicochemical properties. In this connection, crystal-to-crystal transformations can provide a precise visualization of these reactions (Song et al, 2014;Zhang et al, 2014;Li et al, 2015a;Yan et al, 2016;Wang et al, 2017;Zhang et al, 2017).…”

Benzoate‐Induced High‐Nuclearity Silver Thiolate Clusters

“…Thus, the carboxylate should have the ability as a structure‐directing reagent to influence the formation of silver(I) thiolate clusters. However, one disadvantage of introducing carboxylates into silver cluster assembly systems is the low solubility of Ag I ‐carboxylate compounds, which severely impedes the development of carboxylate‐functionalized high‐nuclearity silver(I) thiolate clusters.…”