Cyanide orientational ordering and copper electric field gradients in CuCN·N2H4

Literature Information

Publication Date 2008-12-10
DOI 10.1039/B808266A
Impact Factor 3.676
Authors

Pedro M. Aguiar, Scott Kroeker


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Abstract

The measurement of residual dipolar coupling in 13C and 15N MAS spectra of CuCN·N2H4 allows for the extraction of 63/65Cu quadrupole coupling constants (CQ(63Cu) = 26 ± 4 MHz). Ab initio calculations were employed to determine electric field gradient and chemical shielding tensor orientations, which proved essential for the reliable analyses of residual dipolar coupled 13C and 15N MAS spectra. The 1J(63Cu,13C) and 1J(63Cu,15N) couplings (590 and −120 Hz, respectively) indicate that the cyanide ligands are static and their magnitudes reflect the deviation of the C–Cu–N angle when compared with other copper cyanides. The observed 13C and 15N spectra are most compatible with a structural model wherein the cyanides are fully orientationally ordered: [–Cu–C–N–Cu–C–N–].

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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