Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Abstract

Crystalline cluster-assembled materials (CAMs) are emerging as types of exploratory fabrications due to their atomically precise structures and intriguing chemical/physical properties, as well as their luminescent function. However, constructing novel luminescent porous crystalline CAMs present an enduring and significant challenge owing to their instability and poor ambient-temperature photoluminescent quantum yields. In this work, we synthesized successfully, a mesoporous crystalline CAM (1 ⊃ DMAC), based on silver-chalcogenolate cluster and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE) ligand, with highsymmetry structure and ultralarge pores. 1 ⊃ DMAC exhibited adjustable intense luminescence, originating from aggregation-induced emission (AIE) properties of the TPPE ligand. The diameter of the cubic cage in 1 ⊃ DMAC was as high as 32 Å, which endowed it with satisfactory encapsulation capacity for different guest molecules. Interestingly, by adjusting functionalized guest molecules, circularly polarized luminescence, white-light-emitting, and room-temperature phosphorescence were readily realized. 1 ⊃ DMAC could enrich limited kinds of mesoporous crystalline CAMs and offers the prospect of application in host-guest chemistry. More importantly, this work provides a strategy, versatile for tailoring luminescence in crystalline porous materials.

Circularly polarized luminescence of agglomerate emitters

“…In 2019, Zang et al synthesized mesoporous crystalline silverchalcogenolate cluster-assembled materials through a system of achiral luminous host (MOF)-chiral guest molecules (L/Dmenthol), namely, 1 ⊃ L/D-MT, showing an excellent mirror image Cotton effect (g abs = ±1.1 × 10 −3 ) and CPL emission (g lum = ±1.5 × 10 −3 ) (Figure 8D). [162] F I G U R E 8 (A) Schematic synthesis and molecular simulation of L/D-MOF ⊃ fluorophores. Photographs of the fabricated WLED.…”

“…CPL spectra of 1 ⊃ L/D-MT. Adapted with permission, [162] Copyright 2019, Chinese Chemical Society Some good work is being reported successively. Ma's group achieved the CP phosphorescence in MOF at room temperature.…”

Methanol Dynamically Activated Room-Temperature Phosphorescence from a Twisted 4-Bromobiphenyl System

“…Heavy atoms, such as halides (Cl, Br, and I), 18,19 aromatic carbonyls, 20,21 and some heteroatoms with n electrons, [22][23][24][25][26][27] have been utilized to promote the ISC process. Crystallization, [28][29][30] H-aggregation, 31,32 self-assembling, [33][34][35][36] and embedding organic phosphors in rigid matrix [37][38][39][40][41][42] are commonly used methods for suppressing nonradiative transition.…”

In Situ Capture of a Ternary Supramolecular Cluster in a 58-Nuclei Silver Supertetrahedron

“…Coinage-metal nanoclusters have long been of great interest to researchers in both chemistry and materials fields due to not only their aesthetically appealing structures but also the distinct physicochemical properties across luminescence, catalysis, chirality, electrochemistry and so on. [1][2][3][4][5][6][7][8][9][10][11] Historically, a plethora of atom-precise coinage-metal nanoclusters with thiolates, phosphines and alkynes as protecting ligands have been documented, especially in silver nanocluster family. [12][13][14][15][16] Some prominent examples are Ag 44 , 17 Ag 62 , 18 Ag 180 , 19 Ag 374 , 20 Ag 490 , 21 with the central metal valances of +1 or between 0 and +1.…”