Halogen Bond Induced Structural and Photophysical Properties Modification in Organic–Inorganic Hybrid Manganese Halides

The role of halogen bonding in organic–inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound. In this context, we have synthesized (2-methylbenzimidazolium)­MnCl3(H2O)·H2O (compound 1) crystallizing in a monoclinic space group P21/c wit...

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Published inThe journal of physical chemistry letters Vol. 14; no. 18; pp. 4211 - 4218
Main Authors Panda, Debendra Prasad, Swain, Diptikanta, Sarkar, Sounak, Sundaresan, A.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 11.05.2023
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Physical Insights into Materials and Molecular Properties
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Abstract The role of halogen bonding in organic–inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound. In this context, we have synthesized (2-methylbenzimidazolium)­MnCl3(H2O)·H2O (compound 1) crystallizing in a monoclinic space group P21/c with a 1D infinite chain of edge shared Mn octahedra. In contrast, the chloro-substituted derivative (5-chloro-2-methylbenzimidazolium)2MnCl4 (compound 2) exhibits 0D Mn tetrahedra with a triclinic P1̅ structure. This structural modification from 1D Mn octahedra to 0D Mn tetrahedra involves a unique type-II halogen bonding between organic chlorine (C–Cl) and inorganic chloride (Cl–Mn) ions. Compound 1 exhibits red emission, whereas compound 2 demonstrates dual-band emission, resulting from energy transfer from the organic amine to Mn centers. To rationalize this interesting modulation in structure and photophysical properties, the role of halogen bonding is explored in terms of quantitative electron density analysis and intermolecular interaction energies.
AbstractList The role of halogen bonding in organic-inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound. In this context, we have synthesized (2-methylbenzimidazolium)MnCl (H O)·H O (compound 1) crystallizing in a monoclinic space group 2 / with a 1D infinite chain of edge shared Mn octahedra. In contrast, the chloro-substituted derivative (5-chloro-2-methylbenzimidazolium) MnCl (compound 2) exhibits 0D Mn tetrahedra with a triclinic 1̅ structure. This structural modification from 1D Mn octahedra to 0D Mn tetrahedra involves a unique type-II halogen bonding between organic chlorine (C-Cl) and inorganic chloride (Cl-Mn) ions. Compound 1 exhibits red emission, whereas compound 2 demonstrates dual-band emission, resulting from energy transfer from the organic amine to Mn centers. To rationalize this interesting modulation in structure and photophysical properties, the role of halogen bonding is explored in terms of quantitative electron density analysis and intermolecular interaction energies.
The role of halogen bonding in organic–inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound. In this context, we have synthesized (2-methylbenzimidazolium)­MnCl3(H2O)·H2O (compound 1) crystallizing in a monoclinic space group P21/c with a 1D infinite chain of edge shared Mn octahedra. In contrast, the chloro-substituted derivative (5-chloro-2-methylbenzimidazolium)2MnCl4 (compound 2) exhibits 0D Mn tetrahedra with a triclinic P1̅ structure. This structural modification from 1D Mn octahedra to 0D Mn tetrahedra involves a unique type-II halogen bonding between organic chlorine (C–Cl) and inorganic chloride (Cl–Mn) ions. Compound 1 exhibits red emission, whereas compound 2 demonstrates dual-band emission, resulting from energy transfer from the organic amine to Mn centers. To rationalize this interesting modulation in structure and photophysical properties, the role of halogen bonding is explored in terms of quantitative electron density analysis and intermolecular interaction energies.
Author Panda, Debendra Prasad
Swain, Diptikanta
Sundaresan, A.
Sarkar, Sounak
AuthorAffiliation Center for Materials Crystallography, Department of Chemistry and Interdisciplinary Nanoscience Center (iNANO)
School of Advanced Materials, and Chemistry and Physics of Materials Unit
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  organization: School of Advanced Materials, and Chemistry and Physics of Materials Unit
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Snippet The role of halogen bonding in organic–inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound....
The role of halogen bonding in organic-inorganic hybrid (OIH) halides was seldom investigated despite its potential to enhance the stability of the compound....
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Title Halogen Bond Induced Structural and Photophysical Properties Modification in Organic–Inorganic Hybrid Manganese Halides
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