Hybrid structures formed by homo- and heteroleptic aliphatic dicarboxylates of lead with 2-D inorganic connectivity

Thirumurugan, A.; Rao, C. N. R.

doi:10.1016/j.jssc.2008.02.021

Cited by 17 publications

(10 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The longer linear dicarboxylates have previously been shown to be able to accommodate higher torsion angles in framework structures than their shorter analogues and this is also likely to play a significant role in the differences in the structures adopted by compounds in the Mn 2 (CO 2 (CH 2 ) n CO 2 )(OH) 2 series. 28,31 Despite a number of differences in the four compounds discussed in this series, the MnO x polyhedra are either significantly distorted octahedra or have five-fold coordination. This suggests that, as was previously seen in the Mn(CO 2 (CH 2 ) 2 CO 2 ) compound synthesised by Saines et al, 10 the high spin d 5 electronic configuration of Mn 2+ may play an important role in allowing these unusual structures to form.…”

Section: Resultsmentioning

confidence: 99%

“…By analogy with the terminology used to describe coordination in phosphonate frameworks, the dicarboxylates in this phase are described as having (1212) connectivity. 27,28 This indicates that the two carboxylate groups in the ligand have one oxygen atom that is bonded to one metal while the other oxygen atom is coordinated to two different Mn cations (see Fig. S2a †).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO2)(OH)2 and Mn4(CO2(CH2)nCO2)3(OH)2

2011

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO2)(OH)2 and Mn4(CO2(CH2)nCO2)3(OH)2

2011

View full text Add to dashboard Cite

“…23 The structures of aliphatic lead dicarboxylate metal-organic frameworks have also been reported. 6 The ligand coordination number and geometry around Pb(II) are quite diverse, with at least five different coordination polyhedra reported in the literature where the coordination numbers vary anywhere between 2 and 10. 24 The electron configuration of Pb(II) entails a 6s 2 lone pair.…”

Section: Introductionmentioning

confidence: 99%

“…14 Pb(II) compounds are hemidirected for low coordination numbers (2-5) and holodirected for high coordination numbers (9 and 10), but for intermediate coordination numbers (6)(7)(8), examples of both types of stereochemistry have been reported. 6,20,25 Ab initio molecular orbital calculations and a survey of published structures have identified the primary factors determining coordination geometry. 14,26 Hemidirected geometry is favored if the ligand coordination number is low, the ligands are hard, and there are attractive interactions between the ligands.…”

Section: Introductionmentioning

confidence: 99%

Coordination geometry of lead carboxylates – spectroscopic and crystallographic evidence

et al. 2015

View full text Add to dashboard Cite

Despite their versatility, only a few single-crystal X-ray structures of lead carboxylates exist, due to difficulties with solubility. In particular, the structures of long-chain metal carboxylates have not been reported. The lone electron pair in Pb(ii) can be stereochemically active or inactive, leading to two types of coordination geometries commonly referred to as hemidirected and holodirected structures, respectively. We report (13)C and (207)Pb solid-state NMR and infrared spectra for a series of lead carboxylates, ranging from lead hexanoate (C6) to lead hexadecanoate (C18). The lead carboxylates based on consistent NMR parameters can be divided in two groups, shorter-chain (C6, C7, and C8) and longer-chain (C9, C10, C11, C12, C14, C16, and C18) carboxylates. This dichotomy suggests two modes of packing in these solids, one for the short-chain lead carboxylates and one for long-chain lead carboxylates. The consistency of the (13)C and (207)Pb NMR parameters, as well as the IR data, in each group suggests that each motif represents a structure characteristic of each subgroup. We also report the single-crystal X-ray diffraction structure of lead nonanoate (C9), the first single-crystal structure to have been reported for the longer-chain subgroup. Taken together the evidence suggests that the coordination geometry of C6-C8 lead carboxylates is hemidirected, and that of C9-C14, C16 and C18 lead carboxylates is holodirected.

show abstract

“…Nonetheless, when dicarboxylic acids with different lengths are introduced, the longer organic anion can expand the lattice distances in the organic sheets, while the shorter organic anion would relax the lattice and provide extra space. The relaxation against structural distortion ensures the entrance of large ions such as Cs + and Br − . As a result, the Cs + could eventually be incorporated into the lattice of the 2D Pb(II) coordination compound, enabling the lattice to assemble into a low‐dimensional perovskite structure.…”

mentioning

confidence: 99%

A Strategy toward New Low‐Dimensional Hybrid Halide Perovskites with Anionic Spacers

Zhao

Zhang

et al. 2019

Small

View full text Add to dashboard Cite

Recently, the organic-inorganic halide perovskite (OIHP) materials have received enormous attention due to their unique performances demonstrated in photovoltaic and optoelectronic devices. [1] The perovskite solar cells employing OIHP as absorber with planer structure have demonstrated the certified power conversion efficiency over 23.3%. [2] Holding this great promise, along with their solutionprocessable feature, the research on OIHP materials has been extended to the nanoscale. Both OIHP and all-inorganic halide perovskite (AIHP) nanocrystals (NCs) stand out as a new class of fluorescent light-emitting materials, showing strong quantum confinement effect. [3] Therefore, it is highly expected that the perovskite-based NCs may allow us to fabricate devices with unique photophysical, electronic, and charge transport performances in contrast to their bulk form. [4] The crystallographic dimensionality of the halide perovskite materials can be regulated by adjusting the connection patterns of the PbX 6 octahedron. Taking Cs-based AIHP as an example, the dimensionality can be modulated among 0D, [5] 1D, [6] 2D, [7] and 3D. [8] Compared with the 3D halide perovskite, the low-dimensional counterpart displays abundant structural diversity and functionality not only in halide perovskite but also in the oxide perovskite. [9] It results in improved performance by combining their merits in physiochemical and optoelectronic properties. [10] So far, various organic/inorganic cationic molecules, including ammonium, [11] amidinium, [12] imidazolium, [13] phosphonium, [14] etc., have been used as periodic spacers or ligands to inhibit the formation of 3D perovskite structure by replacing the A-site ions (e.g., Cs + , CH 3 NH 3 + , and HC(NH) 2+ ). In addition, Gemini-type bifunctional molecules with two ionic terminal groups serving as linkers between layers, such as diamine, [15] amino acid, [16] etc., have also been reported to obtain the layered 2D perovskite with extra functionalities. Recently, the 2D Pb 2 X 2 (HDA) (X = F, Cl, and Br) reported by Fei and coworkers indicates that Pb 2+ and halide ions can form a [PbX] − inorganic layer between the organic anionic spacers. [17] However, there have been limited investigations on organic anions serving as the spacers to construct low-dimensional halide perovskite.The low-dimensional halide perovskites have received enormous attention due to their unique photovoltaic and optoelectronic performances. Periodic spacers are used to inhibit the growth of 3D perovskite and fabricate a 2D counterpart with layered structure, mostly based on organic/inorganic cations. Herein, by introducing organic anions (e.g., pentanedioic acid (PDA) and hexanedioic acid (HDA) simultaneously), leaf-shaped (Cs 3 Pb 2 Br 5 ) 2 (PDA-HDA) microplates with low-dimensional structure are synthesized. They also exhibit significant photoluminescence (PL) centered at 540 nm with a narrow emission peak. The synthesis of single crystals of Pb(PDA) and Pb(HDA) allows to further clarify the crystal struct...

show abstract

Hybrid structures formed by homo- and heteroleptic aliphatic dicarboxylates of lead with 2-D inorganic connectivity

Cited by 17 publications

References 53 publications

Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO2)(OH)2 and Mn4(CO2(CH2)nCO2)3(OH)2

Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO2)(OH)2 and Mn4(CO2(CH2)nCO2)3(OH)2

Coordination geometry of lead carboxylates – spectroscopic and crystallographic evidence

A Strategy toward New Low‐Dimensional Hybrid Halide Perovskites with Anionic Spacers

Contact Info

Product

Resources

About