Unveiling the Nature and Strength of Selenium-Centered Chalcogen Bonds in Binary Complexes of SeO 2 with Oxygen-/Sulfur-Containing Lewis Bases: Insights from Theoretical Calculations.

Publisher: MDPI Country of Publication: Switzerland NLM ID: 101092791 Publication Model: Electronic Cited Medium: Internet ISSN: 1422-0067 (Electronic) Linking ISSN: 14220067 NLM ISO Abbreviation: Int J Mol Sci Subsets: MEDLINE

Original Publication: Basel, Switzerland : MDPI, [2000-

Lewis Bases*/chemistry ; Chalcogens*/chemistry ; Selenium*/chemistry ; Sulfur*/chemistry ; Oxygen*/chemistry; Models, Molecular ; Hydrogen Bonding ; Selenium Oxides/chemistry ; Thermodynamics

Among various non-covalent interactions, selenium-centered chalcogen bonds (SeChBs) have garnered considerable attention in recent years as a result of their important contributions to crystal engineering, organocatalysis, molecular recognition, materials science, and biological systems. Herein, we systematically investigated π-hole-type Se ∙∙∙ O/S ChBs in the binary complexes of SeO 2 with a series of O-/S-containing Lewis bases by means of high-level ab initio computations. The results demonstrate that there exists an attractive interaction between the Se atom of SeO 2 and the O/S atom of Lewis bases. The interaction energies computed at the MP2/aug-cc-pVTZ level range from -4.68 kcal/mol to -10.83 kcal/mol for the Se ∙∙∙ O chalcogen-bonded complexes and vary between -3.53 kcal/mol and -13.77 kcal/mol for the Se ∙∙∙ S chalcogen-bonded complexes. The Se ∙∙∙ O/S ChBs exhibit a relatively short binding distance in comparison to the sum of the van der Waals radii of two chalcogen atoms. The Se ∙∙∙ O/S ChBs in all of the studied complexes show significant strength and a closed-shell nature, with a partially covalent character in most cases. Furthermore, the strength of these Se ∙∙∙ O/S ChBs generally surpasses that of the C/O-H ∙∙∙ O hydrogen bonds within the same complex. It should be noted that additional C/O-H ∙∙∙ O interactions have a large effect on the geometric structures and strength of Se ∙∙∙ O / S ChBs. Two subunits are connected together mainly via the orbital interaction between the lone pair of O/S atoms in the Lewis bases and the BD*(OSe) anti-bonding orbital of SeO 2 , except for the SeO 2 ∙∙∙ HCSOH complex. The electrostatic component emerges as the largest attractive contributor for stabilizing the examined complexes, with significant contributions from induction and dispersion components as well.

J Phys Chem A. 2015 Apr 9;119(14):3518-27. (PMID: 25797149)
J Mol Graph. 1996 Feb;14(1):33-8, 27-8. (PMID: 8744570)
Chemphyschem. 2020 Jan 3;21(1):26-31. (PMID: 31823488)
J Mol Model. 2008 Aug;14(8):659-65. (PMID: 18317819)
Biol Chem. 2007 Oct;388(10):997-1006. (PMID: 17937613)
J Phys Chem A. 2019 Jul 18;123(28):5995-6002. (PMID: 31268326)
J Am Chem Soc. 2021 Dec 8;143(48):20207-20215. (PMID: 34818002)
ACS Chem Biol. 2016 Apr 15;11(4):821-41. (PMID: 26949981)
J Pept Sci. 2005 Apr;11(4):187-214. (PMID: 15782428)
J Mol Model. 2019 Jan 4;25(1):19. (PMID: 30610397)
Chemphyschem. 2009 Dec 7;10(17):3013-20. (PMID: 19847843)
J Mol Model. 2017 May;23(5):162. (PMID: 28412768)
J Med Chem. 2015 Jun 11;58(11):4383-438. (PMID: 25734370)
Phys Chem Chem Phys. 2018 Feb 14;20(7):5227-5234. (PMID: 29399687)
Chemphyschem. 2023 Aug 1;24(15):e202300124. (PMID: 37183766)
J Chem Theory Comput. 2017 Jul 11;13(7):3185-3197. (PMID: 28489372)
Inorg Chem. 2007 Mar 19;46(6):2249-60. (PMID: 17311376)
Int J Mol Sci. 2022 Nov 29;23(23):. (PMID: 36499302)
Chemphyschem. 2015 Aug 24;16(12):2496-517. (PMID: 26118675)
Org Biomol Chem. 2022 Jul 20;20(28):5551-5557. (PMID: 35791825)
Chemphyschem. 2018 Oct 5;19(19):2540-2548. (PMID: 30003638)
Phys Chem Chem Phys. 2023 Apr 26;25(16):11286-11300. (PMID: 37066676)
Chem Rev. 2018 Feb 28;118(4):2010-2041. (PMID: 29420879)
J Comput Chem. 2019 Dec 15;40(32):2868-2881. (PMID: 31518004)
Int J Mol Sci. 2023 Aug 22;24(17):. (PMID: 37685843)
Acc Chem Res. 2021 Oct 19;54(20):3906-3916. (PMID: 34606230)
Nat Commun. 2023 Oct 10;14(1):6347. (PMID: 37816750)
Phys Chem Chem Phys. 2021 Aug 28;23(32):17656-17662. (PMID: 34373871)
Chem Soc Rev. 2024 Jan 22;53(2):586-605. (PMID: 38059482)
J Comput Chem. 2012 Feb 15;33(5):580-92. (PMID: 22162017)
J Phys Chem Lett. 2017 Feb 16;8(4):794-800. (PMID: 28145117)
Int J Mol Sci. 2023 Nov 10;24(22):. (PMID: 38003384)
J Am Chem Soc. 2004 Apr 28;126(16):5309-17. (PMID: 15099116)
Magn Reson Chem. 2011 Nov;49(11):740-8. (PMID: 22002712)
Int J Mol Sci. 2022 Apr 10;23(8):. (PMID: 35457005)
Eur J Med Chem. 2021 Nov 5;223:113621. (PMID: 34217061)
ACS Omega. 2023 Aug 30;8(36):32828-32837. (PMID: 37720791)
Acc Chem Res. 2024 Feb 6;57(3):362-374. (PMID: 38275221)
Angew Chem Int Ed Engl. 2008;47(52):10114-8. (PMID: 19016277)
Phys Chem Chem Phys. 2017 Sep 13;19(35):24179-24187. (PMID: 28840208)
J Phys Chem A. 2009 May 14;113(19):5806-12. (PMID: 19382751)
Chemistry. 2015 Apr 27;21(18):6793-800. (PMID: 25766307)
J Am Chem Soc. 2017 Oct 25;139(42):15160-15167. (PMID: 28985065)
Chem Commun (Camb). 2015 Sep 28;51(75):14255-8. (PMID: 26263890)
Acc Chem Res. 2019 May 21;52(5):1313-1324. (PMID: 31082186)
Chem Rev. 2016 May 11;116(9):5072-104. (PMID: 26886515)
J Am Chem Soc. 2010 May 12;132(18):6498-506. (PMID: 20394428)
ACS Chem Biol. 2021 Sep 17;16(9):1622-1627. (PMID: 34477364)
Chem Rev. 2010 Jul 14;110(7):4357-416. (PMID: 20384363)
Acc Chem Res. 2020 Aug 18;53(8):1580-1592. (PMID: 32677432)
J Chem Phys. 2014 Mar 7;140(9):094106. (PMID: 24606352)
Nat Prod Rep. 2002 Dec;19(6):693-718. (PMID: 12521265)
Chem Asian J. 2021 Aug 16;16(16):2351-2360. (PMID: 34214252)
Chembiochem. 2022 Jan 19;23(2):e202100498. (PMID: 34693623)
J Mol Model. 2016 Jan;22(1):29. (PMID: 26755190)
Molecules. 2018 Mar 19;23(3):. (PMID: 29562728)
Acc Chem Res. 2023 Mar 7;56(5):608-621. (PMID: 36802469)

22263003 the National Natural Science Foundation of China; ZK2024-145, ZK2022-369, ZK2022-406 the Natural Science Foundation of Guizhou Province; 2022-188 the Scientific Research Project (Youth Project) of Guizhou Colleges and Universities; KY2022-222 the Youth Science and Technology Talents Growth Project of Guizhou Ordinary Colleges and Universities; gzwkj2022-513 the Science and Technology Fund Project of Guizhou Provincial Health Commission; J[2021]005, J[2021]006, J[2021]039 the High-Level Talent Initiation Project of Guizhou Medical University

Keywords: binary clusters; chalcogen bonds; quantum chemical calculations; π–hole interactions

0 (Lewis Bases)
0 (Chalcogens)
H6241UJ22B (Selenium)
70FD1KFU70 (Sulfur)
S88TT14065 (Oxygen)
0 (Selenium Oxides)

Date Created: 20240619 Date Completed: 20240619 Latest Revision: 20240620

20240620

PMC11171880

10.3390/ijms25115609

38891796