Mechanical properties and peculiarities of molecular crystals
In the last century, molecular crystals functioned predominantly as a means for determining the molecular structures via X-ray diffraction, albeit as the century came to a close the response of molecular crystals to electric, magnetic, and light fields revealed that the physical properties of molecu...
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| Published in | Chemical Society reviews Vol. 52; no. 9; pp. 398 - 3169 |
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| Main Authors | , , , , , , , , , , , , , , , , , , , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
09.05.2023
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| Subjects | |
| Online Access | Get full text |
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| Summary: | In the last century, molecular crystals functioned predominantly as a means for determining the molecular structures
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X-ray diffraction, albeit as the century came to a close the response of molecular crystals to electric, magnetic, and light fields revealed that the physical properties of molecular crystals were as rich as the diversity of molecules themselves. In this century, the mechanical properties of molecular crystals have continued to enhance our understanding of the colligative responses of weakly bound molecules to internal frustration and applied forces. Here, the authors review the main themes of research that have developed in recent decades, prefaced by an overview of the particular considerations that distinguish molecular crystals from traditional materials such as metals and ceramics. Many molecular crystals will deform themselves as they grow under some conditions. Whether they respond to intrinsic stress or external forces or interactions among the fields of growing crystals remains an open question. Photoreactivity in single crystals has been a leading theme in organic solid-state chemistry; however, the focus of research has been traditionally on reaction stereo- and regio-specificity. However, as light-induced chemistry builds stress in crystals anisotropically, all types of motions can be actuated. The correlation between photochemistry and the responses of single crystals-jumping, twisting, fracturing, delaminating, rocking, and rolling-has become a well-defined field of research in its own right: photomechanics. The advancement of our understanding requires theoretical and high-performance computations. Computational crystallography not only supports interpretations of mechanical responses, but predicts the responses itself. This requires the engagement of classical force-field based molecular dynamics simulations, density functional theory-based approaches, and the use of machine learning to divine patterns to which algorithms can be better suited than people. The integration of mechanics with the transport of electrons and photons is considered for practical applications in flexible organic electronics and photonics. Dynamic crystals that respond rapidly and reversibly to heat and light can function as switches and actuators. Progress in identifying efficient shape-shifting crystals is also discussed. Finally, the importance of mechanical properties to milling and tableting of pharmaceuticals in an industry still dominated by active ingredients composed of small molecule crystals is reviewed. A dearth of data on the strength, hardness, Young's modulus, and fracture toughness of molecular crystals underscores the need for refinement of measurement techniques and conceptual tools. The need for benchmark data is emphasized throughout.
Molecular crystals have shown remarkable adaptability in response to a range of external stimuli. Here, we survey this emerging field and provide a critical overview of the experimental, computational and instrumental tools being used to design and apply such materials. |
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| Bibliography: | Durga Prasad Karothu obtained his PhD with T. N. Guru Row from the Indian Institute of Science, Bangalore. He has been a visiting researcher with P. Coppens at the University of Buffalo (USA) and with R. E. Dinnebier at the Max Planck Institute for Solid State Research in Stuttgart (Germany). He was the recipient of the Rising Star Award from the Asian Crystallographic Association (AsCA) for the year 2022. He is currently a senior research scientist in the Naumov Group at New York University Abu Dhabi. His research focuses on the development of organic-based smart materials, organic solid-state chemistry, photocrystallography, and electron diffraction. Shodai Hasebe obtained his BSc degree from Waseda University in 2020. He is currently a graduate student in the research group of Dr Hideko Koshima at Waseda University. His research focuses on mechanically responsive molecular crystals and the application of mechanical crystals to actuators and soft robots. Changquan Calvin Sun is a professor of pharmaceutics at the University of Minnesota, USA. Professor Sun's research focuses on the efficient formulation and design of high-quality tablet products through the appropriate application of materials science and engineering principles. Two main areas of his current research are: (1) crystal and particle engineering for superior pharmaceutical properties; and (2) fundamental understanding of pharmaceutical processes, including powder compaction. He is a Fellow of the American Association for the Advancement of Science (AAAS), the American Association of Pharmaceutical Scientists (AAPS), and the Royal Society of Chemistry (RSC). Rajadurai Chandrasekar is a professor of chemistry and associated with the Center for Nanotechnology at the University of Hyderabad, India. He earned a PhD from the Max Planck Institute for Polymer Research at Mainz. He worked as a postdoctoral researcher in the Institute of Nanotechnology at the Karlsruhe Institute of Technology. His research currently focuses on organic- and polymer-based optically linear and nonlinear photonic components and their integrated circuits. His recent research interests include the micromanipulation of photonic structures using atomic force microscopy (mechanophotonics). Daichi Kitagawa received his PhD degree from Osaka City University in 2014. In 2014-2015, he was engaged as a postdoctoral researcher at JSPS. In 2015, he was promoted to an assistant professor at Osaka City University, and he was promoted to a senior professor in 2019. His current research focuses on the fabrication of novel photochromic molecules, photomechanical crystalline materials, and photoreaction dynamics in crystalline states. Christopher J. Bardeen received his PhD degree from UC Berkeley in 1995. After a postdoctoral fellowship at University of California, San Diego, he became an assistant professor at the University of Illinois, Urbana-Champaign, in 1998. In 2005, he moved to the University of California, Riverside. His current research interest focuses on spectroscopy, photochemistry, and mechanical dynamics in organic materials. Mr Linfeng Lan received his BS degree in chemistry from Jilin University in 2019. Currently, he is a PhD student at Jilin University under the supervision of Prof. Dr Hongyu Zhang. His research interests focus on the optical and mechanical properties of organic crystals and the application of organic crystalline materials in combination with polymers. Marieh Al-Handawi earned her PhD in chemistry and materials science from New York University's Graduate School of Arts and Sciences in 2022. She is currently working as a postdoctoral associate in Naumov's Smart Materials Lab at New York University Abu Dhabi, where she is involved in various interdisciplinary projects related to the design, fabrication, and characterization of materials. Her main research interest is focused on the intersection between materials science and biology, where she investigates natural phenomena with possible applications to materials science, such as biomineralization, water harvesting technologies, and bioluminescence, and applies the underlying principles to bioinspired artificial materials. Pan e Naumov is a tenured professor at New York University Abu Dhabi, with a cross-appointment at NYU's Molecular Design Institute, and a director of the Center for Smart Engineering Materials. He is a native of Macedonia, where he got a BSc degree from Ss. Cyril and Methodius University. After acquiring his PhD in chemistry and materials science from the Tokyo Institute of Technology in 2004, Dr Naumov continued his research at the National Institute for Materials Science, Osaka University and Kyoto University. The research in his group is related to materials science, focusing on smart materials, crystallography, bioluminescence, and petroleomics. Alexander G. Shtukenberg received a specialist degree in 1993 from the Geological Faculty of Saint Petersburg State University, Russia. Under the supervision of Yuri Punin, he received a Candidate of Science degree in 1997 and continued to work at the Geological Faculty as a researcher and faculty member. In 2009, he earned the Doctor of Science degree, and in 2010, he became a professor at the same university. Since 2010, he has been associated with the Molecular Design Institute in the Department of Chemistry at New York University and is currently a research professor. Dr Hideko Koshima was a professor at Ehime University, and in 2014, she moved to Waseda University. Her research interests are in solid-state organic photochemistry, chiral chemistry, and microwave chemistry. Over the last decade, her research had focused on mechanical molecular crystals that are actuated by light and heat. In 2001, she received the Japanese Woman Scientists Association Award, and in 2014, she received the Japanese Photochemistry Association Award for Distinguished Contribution to Photochemistry. Ying Diao is an associate professor, I. C. Gunsalus Scholar and Dow Chemical Company Faculty Scholar at the University of Illinois at Urbana-Champaign. She received PhD from MIT in 2011, and pursued postdoctoral training at Stanford University from 2011 to 2014. Her research group, started in 2015 at Illinois, focuses on understanding the assembly of organic functional materials and innovating printing approaches that enable structural control down to a molecular and nanoscale. She was named an MIT Technology Review Innovators Under 35, a recipient of the NSF CAREER Award, NASA Early Career Faculty Award, and Sloan Fellowship in Chemistry. Tamador Alkhidir is a visiting researcher in the Advanced Materials Chemistry Center (AMCC) at Khalifa University and also works as a curriculum specialist in the UAE Ministry of Education. She received her PhD from Khalifa University in 2020. Her research interests are focused on the applications of computational materials modelling for gaining a better understanding of structure-property correlations. She is an expert in the simulation of the electrical and mechanical properties of organic and inorganic materials using DFT methods. Gonzalo Campillo-Alvarado is an assistant professor of chemistry at Reed College in Portland, OR, USA. His research focuses on designing dynamic crystalline materials with an emphasis on boron for applications in chemical separations, pharmaceutics, and electronics. Before joining Reed, he was an Illinois Distinguished Postdoctoral Research Associate at the University of Illinois at Urbana-Champaign, mentored by Prof. Ying Diao. He received his PhD in chemistry from the University of Iowa (advisor: Prof. Leonard R. MacGillivray), his MSc in chemistry at Universidad Autónoma del Estado de Morelos, and his BSc in biopharmaceutical chemistry at Universidad Veracruzana. Prof. Dr Hongyu Zhang received his PhD in 2006 at Jilin University, majoring in organic chemistry. He joined Prof. Shigehiro Yamaguchi's group at Nagoya University as a JSPS postdoctoral fellow (2006-2008). In 2008, he joined the faculty of Jilin University as an associate professor of chemistry and was promoted to full professor in 2014. His main research interests focus on the design and synthesis of organic functional materials and their applications in optoelectronics. He received a number of awards and honors, including the NSFC outstanding Young Scholar Award (2017) and the CCS Lectureship Award for Creative Young Supramolecular Chemists (2020). Sharmarke Mohamed is an Associate Professor of Chemistry, theme leader in the Advanced Materials Chemistry Center (AMCC), and PI of the Green Chemistry and Materials Modelling Laboratory at Khalifa University. In 2011, he received his PhD from UCL. His PhD research focused on small molecule X-ray crystallography and computational methods of crystal structure prediction. He has worked in the pharmaceutical industry as an experimental drug development chemist and is an inventor on a number of patents. Since joining the faculty at Khalifa University in 2014, he has widened his research interests to cover mechanochemistry, multiscale materials modeling and green chemistry. Mubarak Almehairbi is an MSc student in the Applied Chemistry program at Khalifa University. He completed his BSc chemistry capstone project under the supervision of Prof. Sharmarke Mohamed. During this capstone project, he was successful in developing a code to better understand and predict the mechanical properties of organic molecular crystals using DFT methods. In his current role as an MSc student, his research is focused on the computational prediction of the vibrational-rotational spectra of diatomic radicals found in the Martian atmosphere. Mubarak has an ongoing passion for code development and in the application of machine learning methods to better understand and predict materials properties. Seiya Kobatake is professor of materials chemistry at Osaka Metropolitan University in Japan. He received his PhD degree from Osaka City Universit ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 ObjectType-Review-3 content type line 23 |
| ISSN: | 0306-0012 1460-4744 1460-4744 |
| DOI: | 10.1039/d2cs00481j |