Ligand-Driven Coordination Sphere-Induced Engineering of Hybride Materials Constructed from PbCl₂ and Bis-Pyridyl Organic Linkers for Single-Component Light-Emitting Phosphors

Abstract

We report design and structural characterization of six new coordination polymers fabricated from PbCl and a series of closely related bis-pyridyl ligands L and HL-HL, namely, [Pb(L)Cl], [Pb(HL)Cl]·nMeOH, [Pb(HL)Cl]·0.5 nMeOH, [Pb(L)Cl], [Pb(HL)Cl], and [Pb(L)Cl]·nMeOH. The topology of the obtained networks is dictated by the geometry of the organic ligand. The structure of [Pb(L)Cl] is constructed from the [PbCl] two-dimensional (2D) sheets, linked through organic linkers into a three-dimensional framework, which exhibits a unique binodal 4,7-connected three-periodic topology named by us as sda1. Topological analysis of the 2D metal-organic sheet in [Pb(HL)Cl]·nMeOH discloses a binodal 3,4-connected layer topology, regardless of the presence of tetrel bonds. A one-dimensional (1D) coordination polymer [Pb(HL)Cl]·0.5 nMeOH is considered as a uninodal 2-connected chain. The overall structure of [Pb(L)Cl] is constructed from dimeric tetranuclear [Pb(μ-L-κN:N':N″:μ-O)(μ-Cl)(μ-Cl)] cationic blocks linked in a zigzag manner through bridging μ-Cl ligands, yielding a 1D polymeric chain. Topological analysis of this chain reveals a unique pentanodal 3,4,4,5,6-connected chain topology named by us as sda2. The structure of [Pb(HL)Cl] exhibits a 1D zigzaglike polymeric chain. Two chains are further linked into a 1D gridlike ribbon through the dimeric [Pb(μ-Cl)Cl] blocks as bridging nodes. With the bulkiest ligand HL, a 2D layered coordination polymer [Pb(L)Cl]·nMeOH is formed, which network, considering all tetrel bonds, reveals a unique heptanodal 3,3,3,3,4,5,5-connected layer topology named by us as sda3. Compounds [Pb(L)Cl], [Pb(L)Cl], and [Pb(HL)Cl] were found to be emissive in the solid state at ambient temperature. While blue emission of [Pb(L)Cl] is due to the ligand-centered transitions, bluish-green and white luminescence of [Pb(L)Cl] and [Pb(HL)Cl], respectively, was assigned to ligand-to-metal charge transfer mixed with metal-centered excited states. Molecular as well as periodic calculations were additionally applied to characterize the obtained polymers.

Crystal structure and Hirshfeld surface analysis of 5-(3,5-di-tert-butyl-4-hydroxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazole-1-carboxamide

“…Non-covalent bond donor/acceptor properties of pyrazoles or related N-compounds are crucial in the organization of supramolecular architectures in the solid state and hence their catalytic activity, solubility, etc. (Ma et al, 2017;Maharramov et al, 2010;Mahmoudi et al, 2016Mahmoudi et al, , 2017aMahmoudi et al, ,b, 2018aMahmudov et al, 2014Mahmudov et al, , 2019Shikhaliyev et al, 2018). As part of a further study of this class of compounds, the crystal structure and Hirshfeld surface analysis of the title compound, 5-(3,5-di-tert-butyl-4-hydroxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazole-1-carboxamide, are reported on herein.…”

Tetrel Bonding and Other Non-Covalent Interactions Assisted Supramolecular Aggregation in a New Pb(II) Complex of an Isonicotinohydrazide

“…The hemidirected coordination allows Pb(II) to participate in the formation of tetrel bonds, which are of great importance for the resulting topology of Pb(II) coordination compounds [ 17 , 19 , 22 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. Although the occurrence of hemidirected or holodirected bonding cannot be reliably predicted [ 19 , 28 , 29 , 30 , 31 , 40 , 41 ], recent work using polyfunctional multidentate ligands, such as carboxylates of 2-thiols or heterocycles [ 19 , 24 , 25 , 26 , 27 , 28 ], or the per se polyfunctional thiothiosemicarbazones, hydrazones, or Schiff base ligands of the salen or salan type [ 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ] allowed formation of tetrel bonds. We also have recentl...…”

Supramolecular Assemblies in Pb(II) Complexes with Hydrazido-Based Ligands

“…It is well-known that the 6s 2 electron pair of Pb(II) can either remain inert, or be stereochemically active as widely discussed in the literature [16][17][18][19][20][21][22][23]. Tetrel bond interactions with hemi-directionally coordinated lead have been studied in the literature [24][25][26] and are relevant in supramolecular chemistry [27][28][29] and metal organic frameworks (MOF) based on lead(II) [30].…”