A Mechanochromic and Vapochromic Luminescent Cuprous Complex Based on a Switchable Intramolecular π···π Interaction
Ping Yu1, Dan Peng1, Li-Hua He1
1Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, Department of Materials, Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, People's Republic of China.
Abstract:
An in-depth study on a stimuli-responsive tetranuclear cuprous luminescent complex is reported and gives new insights into the origin and possible use of the observed stimuli-responsive luminescence. Its crystalline polymorphs with two different shapes are obtained by using different crystallization solvents and show distinct emissions, with one being blue emissive and the other being yellow emissive. Upon grinding, only the blue-emitting polymorph has a marked change in the emission color from blue to yellow, and its ground sample exhibits a yellow emission similar to that of the yellow-emitting polymorph. Interestingly, the yellow-emitting polymorph after exposure to acetone vapor can emit a blue emission and display luminescence mechanochromism similar to that of the blue-emitting polymorph. Single-crystal structural analyses of the two different polymorphs reveal the relationship between the mechanochromic luminescence and the geometrical configuration of the {Cu(μ-dppm)2Cu} unit and intramolecular "pyridyl/phenyl" π···π interactions, supported as well by their PXRD, FT-IR, TGA, and PL studies in various states and by TD-DFT analyses. The results demonstrate the different roles of switchable intramolecular π···π interactions and the geometrical configuration of the {Cu(μ-dppm)2Cu} unit in this stimuli-responsive luminescence and potential applications of such stimuli-responsive luminescence in optical sensing and anticounterfeiting encryption technologies and deepen the understanding of such stimuli-responsive luminescence originating from switchable intramolecular π···π interactions. In addition, it is clearly suggested that the rational utilization of switchable intramolecular π···π interactions is a feasible route for developing stimuli-responsive intelligent luminescent materials and devices.
More Related Videos
10:33An Electrochemical Cholesteric Liquid Crystalline Device for Quick and Low-Voltage Color Modulation
Published on: February 27, 2019
14:11Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
Published on: June 10, 2021
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
01:26Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
02:42Valence Bond Theory
01:14Photoluminescence: Applications
02:52Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...