Stereochemically Dependent Synthesis of Two Cu(I) Cluster-Based Coordination Polymers with Thermochromic Luminescence

Abstract

Two Cu(I) cluster based coordination polymers, [CuI(cis-bpype)]·CHCN (1) and [CuI(cis-bpype)(trans-bpype)]·3DMF (2), have been synthesized from cis- and trans-1,2-bis(4-(pyridin-2-yl)phenyl)ethane (cis- and trans-bpype) ligands and {CuI(PPh)} as starting materials. In compound 1, adjacent rhomboid-type {CuI} units from the decomposition of {CuI(PPh)} starting material connect by cis-bpype ligands to form a 1D framework. Compound 2 also has a 1D structure, but it has a {ML}-type coordinated cage constructed by three cis-bpype ligands and two {CuI} secondary building units (SBU), and these coordination cages further link by trans-bpype to form the final frameworks. Upon cooling from 300 to 80 K, these Cu(I) cluster based coordination polymers exhibit interesting thermochromic behavior. In particular, compound 2 gives a chromic process from green luminescence at room temperature to red luminescence at 80 K and its corresponding CIE coordinates shift from green (0.34, 0.43) at 300 K to red (0.46, 0.42) at 80 K, respectively. This red shift of 124 nm (516 to 640 nm) is large enough to ensure a color change visible to the naked eye, which can be potentially utilized as a temperature sensor with a wide range.

Self‐Assembly and Aggregation‐Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles

“…In addition, to support our assignments, Table S1 presents some selected literature reports about the Cu 4 I 4 unit, where we have focused on those bearing phosphines or thiolates as ancillary ligands. A few representative nitrogen donor‐based systems are presented for comparison as well [46–58] …”

Thermo-responsive light-emitting metal complexes and related materials

“…26c-e). 128 Polymer 32 showed reversible thermochromic dual luminescence at 516 and 640 nm. Upon cooling from 300 to 80 K, the original green emission at 516 nm, assigned to the ligand-dominated transition, was moderately enhanced.…”

Design and Property Modulation of Metal–Organic Frameworks with Aggregation-Induced Emission

“…98 Functionalization of TPE with carboxyphenyl and pyridyl group can provide flexible phenyl rings of the TPE core. 99 For example, the MOF (Zn 2 Cl 4 Py-TPE)•4(TCE) exhibited weak emission due to intramolecular motions of TPPE linkers in the framework. By allowing analytes to enter pores, the MOF sensor exhibits enhanced turn-on fluorescence in response to methyl-substituted benzene VOCs caused by the hindrance of the free motion for linkers.…”