Single-Metallic Thermoresponsive Coordination Network as a Dual-Parametric Luminescent Thermometer

Abstract

The single-metallic coordination networks (CNs), simultaneously exhibiting temperature-dependent lifetime (TDLT) and emission band shift (TDEBS), are desirable for application in luminescent thermometers with high accuracy and reliability in a large temperature range. Nonetheless, up to date, there are no reports on such kinds of materials due to the lack of in-depth understanding of the origin of TDLT and TDEBS at a molecule level, being critical for exploiting a universal approach to design a dual-parametric CN phosphorescent thermometer (CN-PT). Herein, we have constructed a thermoresponsive CN [Cu2(L1)­Br2]∞ (IAM21-1, L1 = N 1,N 6-di­(pyridin-3-yl)­adipamide) via a flexible-ligand-implanted strategy. The TDLT and TDEBS properties of IAM21-1 enable it to be applied as a single-metallic dual-parametric CN-PT in 50–500 K, which is the widest temperature range reported so far. The combination of structure analysis and DFT calculations demonstrates that the redshift of the emission band upon the decreasing temperature originates from the reversible skeleton-shrinkage-triggered narrower band gap. This work has unveiled the origin of TDLT and TDEBS properties and proposed an efficient strategy for designing dual-parametric CN-PTs.

Coordination networks constructed from a flexible ligand: single-crystal-to-single-crystal transformations and thermoresponsive and electrochemical performances

“…2 (L1)Br 2 ] ∞ (2a) and [Cu II 2 (L1)Br 2 ] ∞ (2c) 2a was prepared according to a reported literature procedure, 36 and 2c was obtained upon exposure of the yellow crystals of 2a to air for a few days or treating the yellow 2a crystals with 0.05 M H 2 O 2 in ethanol solution for 12 h, being similar to 1a.…”

“…L1 contains N atoms that readily coordinate to transition metal ions, and thus it has been widely used in the construction of various CNs, 36 while 5,5′-(adipoylbis(azanediyl))diisophthalic acid has the same main skeleton of L1, and possesses carboxylate groups that are inert to bind to transition metal ions. Herein, 1a is obtained by the primary and auxiliary mixed flexible ligand method, i.e., L1 is chosen as a primary bridging linker, while L2 is used as an enhancer for the formation of the CN but does not participate in bonding with the Cu(I) metal ions.…”

“…Herein, 1a is obtained by the primary and auxiliary mixed flexible ligand method, i.e., L1 is chosen as a primary bridging linker, while L2 is used as an enhancer for the formation of the CN but does not participate in bonding with the Cu(I) metal ions. 36 Single crystal X-ray diffraction analysis shows that 1a is isostructural to 2a (Tables S1 and S2 †) and crystallizes in the monoclinic space group P2/c with one L1 ligand, two Cu(I) ions and two Cl − anions in the crystallographic minimum asymmetric unit. Fig.…”

Stacking Lanthanide-MOF Thin Films to Yield Highly Sensitive Optical Thermometers

“…Precise and rapid temperature-sensing with contactless readout is a key requirement in science and engineering. − In a continuous effort to improve the performance of such devices, advanced materials and technologies are being developed for applications in various fields, including the monitoring of industry reactions and biological processes, as well as in cryogenics technology. − In this context, temperature sensors with optical readout are of particular interest, since they allow for straightforward integration without the need for electrical contacts. Among the different variants of optical temperature sensors, luminescence-based devices have particularly appealing properties. ,, Appropriate choice of materials allows to determine the temperature directly from the ratio of two emitted intensities. − …”

Self‐assembled Fluorescent Nanoparticles with Tunable LCST Behavior in Water

“…[15] The introduction of both fluorescence and thermo-responsiveness properties into one material shows great potential in real-life applications on account of the interesting fluorescence changes in response to temperature. [16] Herein, we designed and prepared a neutral amphiphile monomer (M), containing a TPE group with two phenyl rings fixed by a covalent bond (FTPE) as a hydrophobic head and TEG chains as hydrophilic tails (Figure 1). Therefore, M can self-assemble into NPs in an aqueous solution.…”