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London Dispersion and Hydrogen-Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes.

ABSTRACT: Diadamantyl ether (DAE, C20 H30 O) represents a good model to study the interplay between London dispersion and hydrogen-bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. In the monomer, C-H???H-C London dispersion attractions between the two adamantyl subunits further stabilize its structure. Water and the alcohol partners bind to diadamantyl ether through hydrogen bonding and non-covalent Owater/alcohol ???H-CDAE and C-Halcohol ???H-CDAE interactions. Electrostatic contributions drive the stabilization of all the complexes, whereas London dispersion interactions become more pronounced with increasing size of the alcohol. Complexes with dominant dispersion contributions are significantly higher in energy and were not observed in the experiment. The results presented herein shed light on the first steps of microsolvation and aggregation of molecular complexes with London dispersion energy donor (DED) groups and the kind of interactions that control them.

SUBMITTER: Quesada Moreno MM

PROVIDER: S-EPMC7497036 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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London Dispersion and Hydrogen-Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes.

Quesada Moreno María Mar MM Pinacho Pablo P Pérez Cristóbal C Šekutor Marina M Schreiner Peter R PR Schnell Melanie M

Chemistry (Weinheim an der Bergstrasse, Germany) 20200727 47

Diadamantyl ether (DAE, C<sub>20</sub> H<sub>30</sub> O) represents a good model to study the interplay between London dispersion and hydrogen-bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. In the monomer, C-H⋅⋅⋅H-C London dispersion attractions between the two adamantyl subunits further stabilize its st ...[more]

PMID: 32428323

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Project description:Synthetic peroxo-bridged high-spin (HS) heme-(μ-η2:η1-O22-)-Cu(L) complexes incorporating (as part of the copper ligand) intramolecular hydrogen-bond (H-bond) capabilities and/or steric effects are herein demonstrated to affect the complex's electronic and geometric structure, notably impacting the spin state. An H-bonding interaction with the peroxo core favors a low-spin (LS) heme-(μ-η1:η1-O22-)-Cu(L) structure, resulting in a reversible temperature-dependent interconversion of spin state (5 coordinate HS to 6 coordinate LS). The LS state dominates at low temperatures, even in the absence of a strong trans-axial heme ligand. Lewis base addition inhibits the H-bond facilitated spin interconversion by competition for the H-bond donor, illustrating the precise H-bonding interaction required to induce spin-crossover (SCO). Resonance Raman spectroscopy (rR) shows that the H-bonding pendant interacts with the bridging peroxide ligand to stabilize the LS but not the HS state. The H-bond (to the Cu-bound O atom) acts to weaken the O-O bond and strengthen the Fe-O bond, exhibiting ν(M-O) and ν(O-O) values comparable to analogous known LS complexes with a strong donating trans-axial ligand, 1,5-dicyclohexylimidazole, (DCHIm)heme-(μ-η1:η1-O22-)-Cu(L). Variable-temperature (-90 to -130 °C) UV-vis and 2H NMR spectroscopies confirm the SCO process and implicate the involvement of solvent binding. Examining a case of solvent binding without SCO, thermodynamic parameters were obtained from a van't Hoff analysis, accounting for its contribution in SCO. Taken together, these data provide evidence for the H-bond group facilitating a core geometry change and allowing solvent to bind, stabilizing a LS state. The rR data, complemented by DFT analysis, reveal a stronger H-bonding interaction with the peroxo core in the LS compared to the HS complexes, which enthalpically favors the LS state. These insights enhance our fundamental understanding of secondary coordination sphere influences in metalloenzymes.

Dataset Information

London Dispersion and Hydrogen-Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes.

Publications

London Dispersion and Hydrogen-Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes.

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