Structural Diversity in Supramolecular Organization of Anionic Phosphate Monoesters: Role of Cations

Biswajit Santra; Debdeep Mandal; Vivek Gupta; Pankaj Kalita; Vierandra Kumar; Ramakirushnan Suriya Narayanan; Atanu Dey; Nicolas Chrysochos; Akbar Mohammad; Ajeet Singh; Michael Zimmer; Rana Dalapati; Shyam Biswas; Carola Schulzke; Vadapalli Chandrasekhar; David Scheschkewitz; Anukul Jana

doi:10.1021/acsomega.8b03192

Structural Diversity in Supramolecular Organization of Anionic Phosphate Monoesters: Role of Cations

ACS Omega. 2019 Jan 29;4(1):2118-2133. doi: 10.1021/acsomega.8b03192. eCollection 2019 Jan 31.

Authors

Biswajit Santra¹, Debdeep Mandal¹, Vivek Gupta¹, Pankaj Kalita², Vierandra Kumar³, Ramakirushnan Suriya Narayanan¹, Atanu Dey¹, Nicolas Chrysochos⁴, Akbar Mohammad⁵, Ajeet Singh⁵, Michael Zimmer⁶, Rana Dalapati⁷, Shyam Biswas⁷, Carola Schulzke⁴, Vadapalli Chandrasekhar^{1

3}, David Scheschkewitz⁶, Anukul Jana¹

Affiliations

¹ Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad 500107, India.
² National Institute of Science Education and Research Bhubaneswar, HBNI, Bhubaneswar 752050, Odisha, India.
³ Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
⁴ Institut für Biochemie, Ernst-Moritz-Arndt Universität Greifswald, Felix-Hausdorff-Straße 4, D-17487 Greifswald, Germany.
⁵ Discipline of Chemistry, Indian Institute of Technology Indore, Simrol, Khandwa Road, Indore 453552, India.
⁶ Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66123 Saarbrücken, Germany.
⁷ Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India.

Abstract

Syntheses and structures of anionic arylphosphate monoesters [ArOP(O)₂(OH)]^- (Ar = 2,6-CHPh₂-4-R-C₆H₂; R = Me/Et/iPr/tBu) with different counter cations are reported. The counter cations were varied systematically: imidazolium cation, 2-methyl imidazolium cation, N-methyl imidazolium cation, N,N'-alkyl substituted imidazolium cation, 1,4-diazabicyclo[2.2.2]octan-1-ium cation, 4,4'-bipyridinium dication, and magnesium(II) dication. The objective was to examine if the supramolecular structure of anionic arylphosphate monoesters could be modulated by varying the cation. It was found that an eight-membered P₂O₄H₂-hydrogen-bonded dimeric motif involving intermolecular H-bonding between the [P(O)(OH)] unit of the anionic phosphate monoester along with the counter cation is formed with 2-methyl imidazolium cation, N-methyl imidazolium cation, N,N'-alkyl substituted imidazolium cation, 1,4-diazabicyclo[2.2.2]octan-1-ium cation, and magnesium(II) dication; both discrete and polymeric H-bonded structures are observed. In the case of imidazolium cations and 1,4-diazabicyclo[2.2.2]octan-1-ium cation, the formation of one-dimensional polymers (single lane/double lane) was observed. On the other hand, two types of phosphate motifs, intermolecular H-bonded dimer and an open-form, were observed in the case of 4,4'-bipyridinium dication.