Prasita Mazumder, Dibyendu Dey, Prasenjit Giri, Souvik Garani, Ranajit Mandal, Ahmad Husain, Manas K. Panda
{"title":"Polymorphism and Substitutional Effect on the Thermoresponsive and Luminescence Properties of Organic Molecular Crystals","authors":"Prasita Mazumder, Dibyendu Dey, Prasenjit Giri, Souvik Garani, Ranajit Mandal, Ahmad Husain, Manas K. Panda","doi":"10.1021/acs.cgd.4c00827","DOIUrl":null,"url":null,"abstract":"Smart molecular crystals that macroscopically respond to various external stimuli such as light, thermal, pressure, or humidity have emerged as potential candidates for their applications as actuators, sensors, optoelectronics, and other machinery devices. These materials have the unique capability to transform stimuli-induced molecular response to bulk-scale property change. Compared to single-stimuli-responsive crystals, developing multistimuli-responsive crystals that can respond differently to various stimuli is a challenging task. In this manuscript, we report a new class of multistimuli-responsive acylhydrazone derivatives in which thermosalient (TS) actuation and solid-state luminescence can be tuned using polymorphism and substitutional variation. The crystals of methyl-substituted compound (<i>N</i>′-(4-(dimethyamino)benzylidene)-4-hydroxybenzohydrazide), <b>NMe</b><sub><b>2</b></sub><b>OH</b>, display prominent TS actuation and bright cyan luminescence in the solid state. On the contrary, two polymorphs of the ethyl-substituted compound (<i>N</i>′-(4-(diethyamino)benzylidene)-4-hydroxybenzohydrazide), <b>NEt</b><sub><b>2</b></sub><b>OH-FL (</b>Fluorescent<b>)</b> and <b>NEt</b><sub><b>2</b></sub><b>OH-NFL</b> (Nonfluorescent), exhibit drastically different thermal and optical responses. While <b>NEt</b><sub><b>2</b></sub><b>OH-FL</b> crystals display fascinating TS actuation and luminescence behavior, the <b>NEt</b><sub><b>2</b></sub><b>OH-NFL</b> crystals are nonthermosalient and nonluminescent. With the aid of the single-crystal, powder X-ray diffraction study, we have established that distinct stimuli-responsive properties of the crystals are rooted in their molecular conformations and crystal packing. Our work provides an effective approach to tune the stimuli-responsive behavior of molecular crystals for various technological applications.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.cgd.4c00827","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Smart molecular crystals that macroscopically respond to various external stimuli such as light, thermal, pressure, or humidity have emerged as potential candidates for their applications as actuators, sensors, optoelectronics, and other machinery devices. These materials have the unique capability to transform stimuli-induced molecular response to bulk-scale property change. Compared to single-stimuli-responsive crystals, developing multistimuli-responsive crystals that can respond differently to various stimuli is a challenging task. In this manuscript, we report a new class of multistimuli-responsive acylhydrazone derivatives in which thermosalient (TS) actuation and solid-state luminescence can be tuned using polymorphism and substitutional variation. The crystals of methyl-substituted compound (N′-(4-(dimethyamino)benzylidene)-4-hydroxybenzohydrazide), NMe2OH, display prominent TS actuation and bright cyan luminescence in the solid state. On the contrary, two polymorphs of the ethyl-substituted compound (N′-(4-(diethyamino)benzylidene)-4-hydroxybenzohydrazide), NEt2OH-FL (Fluorescent) and NEt2OH-NFL (Nonfluorescent), exhibit drastically different thermal and optical responses. While NEt2OH-FL crystals display fascinating TS actuation and luminescence behavior, the NEt2OH-NFL crystals are nonthermosalient and nonluminescent. With the aid of the single-crystal, powder X-ray diffraction study, we have established that distinct stimuli-responsive properties of the crystals are rooted in their molecular conformations and crystal packing. Our work provides an effective approach to tune the stimuli-responsive behavior of molecular crystals for various technological applications.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.