Severity: Warning
Message: file_get_contents(https://...@gmail.com&api_key=61f08fa0b96a73de8c900d749fcb997acc09): Failed to open stream: HTTP request failed! HTTP/1.1 429 Too Many Requests
Filename: helpers/my_audit_helper.php
Line Number: 143
Backtrace:
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 143
Function: file_get_contents
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 209
Function: simplexml_load_file_from_url
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 994
Function: getPubMedXML
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 3134
Function: GetPubMedArticleOutput_2016
File: /var/www/html/application/controllers/Detail.php
Line: 574
Function: pubMedSearch_Global
File: /var/www/html/application/controllers/Detail.php
Line: 488
Function: pubMedGetRelatedKeyword
File: /var/www/html/index.php
Line: 316
Function: require_once
In the study of mononuclear transition metal single molecule magnets (SMMs), extensive research has concentrated on identifying optimal coordination geometries around the central metal ion to enhance SMM properties. However, the role of non-covalent interactions in the second coordination sphere has been relatively underexplored. Here, we study the impact of non-covalent Cl⋯H interactions on the magnetic anisotropy of the central Co(II) ion in the distorted axially compressed octahedral complex CoCl(tu) (1) (tu = SC(NH)). By performing cantilever torque magnetometry on 1, the orientation of the magnetic easy axis is found to deviate by almost 40° from the axial Co-Cl bond. Theoretical modelling on structural modifications of the structure of 1, quantifies how the distance between the Cl ligand and the nearest H-atom significantly influences the orientation of the magnetic easy axis and the -value. Experimental chemical bonding analysis based on multipole modelling of synchrotron X-ray diffraction data on 1 reveal that the nearby H-atoms polarize the electron density of the Cl-ligands. This polarization results in reduced electron density at the axial positions on the Co octahedra, explaining the calculated increase in the magnitude of the -value, when the H-atoms are moved away from Cl . Topological analysis of theoretical electron densities on modified structures of 1 corroborates an increase in the electron density at the Co-Cl bond critical point, as the nearby H-atoms are moved further from Cl. These findings demonstrate the significant influence that non-covalent interactions have on the magnetic anisotropy of mononuclear transition metals and opens the possibility of utilizing these interactions in the design of transition metal based SMMs.
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Source |
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http://dx.doi.org/10.1039/d4dt02873b | DOI Listing |
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