Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions
The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher ele...
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| Format: | Article |
| Language: | English |
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International Union of Crystallography
2017-11-01
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| Series: | IUCrJ |
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| Online Access: | http://scripts.iucr.org/cgi-bin/paper?S2052252517014658 |
| _version_ | 1798031415500079104 |
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| author | Sudhir Mittapalli D. Sravanakumar Perumalla Jagadeesh Babu Nanubolu Ashwini Nangia |
| author_facet | Sudhir Mittapalli D. Sravanakumar Perumalla Jagadeesh Babu Nanubolu Ashwini Nangia |
| author_sort | Sudhir Mittapalli |
| collection | DOAJ |
| description | The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (Cl...Cl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger I...I halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328–333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and non-thermosalient. 3,5-Dibromo- (Compound-B) and 3-bromo-5-chloro- (Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362–365 K). In the case of 3,5-diiodosalinazid (Compound-D) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The di-halogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange. |
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| id | doaj.art-7d1ae4555f2545f3b3e1090024835bf4 |
| institution | Directory Open Access Journal |
| issn | 2052-2525 |
| language | English |
| last_indexed | 2024-04-11T19:57:04Z |
| publishDate | 2017-11-01 |
| publisher | International Union of Crystallography |
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| spelling | doaj.art-7d1ae4555f2545f3b3e1090024835bf42022-12-22T04:05:58ZengInternational Union of CrystallographyIUCrJ2052-25252017-11-014681282310.1107/S2052252517014658ed5012Thermomechanical effect in molecular crystals: the role of halogen-bonding interactionsSudhir Mittapalli0D. Sravanakumar Perumalla1Jagadeesh Babu Nanubolu2Ashwini Nangia3School of Chemistry, University of Hyderabad, Professor C. R. Rao Road, Gachibowli, Hyderabad 500 046, IndiaDepartment of Inorganic and Physical Chemistry, Indian Institute of Science, Bengaluru 500 016, IndiaCSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500 007, IndiaSchool of Chemistry, University of Hyderabad, Professor C. R. Rao Road, Gachibowli, Hyderabad 500 046, IndiaThe design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (Cl...Cl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger I...I halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328–333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and non-thermosalient. 3,5-Dibromo- (Compound-B) and 3-bromo-5-chloro- (Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362–365 K). In the case of 3,5-diiodosalinazid (Compound-D) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The di-halogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange.http://scripts.iucr.org/cgi-bin/paper?S2052252517014658halogen bondshydrogen bondsmaterials sciencepolymorphismsalinazidcrystal engineeringmechanochemistrymolecular crystalsmaterials modelling |
| spellingShingle | Sudhir Mittapalli D. Sravanakumar Perumalla Jagadeesh Babu Nanubolu Ashwini Nangia Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions IUCrJ halogen bonds hydrogen bonds materials science polymorphism salinazid crystal engineering mechanochemistry molecular crystals materials modelling |
| title | Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions |
| title_full | Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions |
| title_fullStr | Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions |
| title_full_unstemmed | Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions |
| title_short | Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions |
| title_sort | thermomechanical effect in molecular crystals the role of halogen bonding interactions |
| topic | halogen bonds hydrogen bonds materials science polymorphism salinazid crystal engineering mechanochemistry molecular crystals materials modelling |
| url | http://scripts.iucr.org/cgi-bin/paper?S2052252517014658 |
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