Words in supramolecular chemistry: the ineffable advances of polyiodide chemistry

Savastano, Matteo

doi:10.1039/d0dt04091f

Cited by 38 publications

(66 citation statements)

References 135 publications

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“…Inset shows (left to right) covalent bond distribution for I 3 – (violet) and interaction distances of I 3 – subunits with generic I 2 probes, either covalent (i.e., pentaiodide proximal bond distances, red) or supramolecular (pink), in order to give an appropriate view of actual broadness of statistical distributions. Reproduced with permission from ref ( 36 ). Copyright 2021 Royal Society of Chemistry.…”

Section: Results and Discussionmentioning

confidence: 99%

Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

et al. 2021

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Polyiodide networks are currently of great practical interest for the preparation of new electronic materials. The participation of metals in the formation of these networks is believed to improve their mechanical performance and thermal stability. Here we report the results on the construction of polyiodide networks obtained using Cu(II) complexes of a series of pyridinol-based tetraazacyclophanes as countercations. The assembly of these crystalline polyiodides takes place from aqueous solutions on the basis of similar structural elements, the [CuL] 2+ and [Cu(H –1 L)] + (L = L2 , L2-Me , L2-Me 3 ) complex cations, so that the peculiarities induced by the increase of N-methylation of ligands, the structural variable of ligands, can be highlighted. First, solution equilibria involving ligands and complexes were analyzed (potentiometry, NMR, UV–vis, ITC). Then, the appropriate conditions could be selected to prepare polyiodides based on the above complex cations. Single-crystal XRD analysis showed that the coordination of pyridinol units to two metal ions is a prime feature of these ligands, leading to polymeric coordination chains of general formula {[Cu(H –1 L)]} n n + (L = L2-Me , L2-Me 3 ). In the presence of the I – /I 2 couple, the polymerization tendency stops with the formation of [(CuL)(CuH –1 L)] 3+ (L = L2-Me , L2-Me 3 ) dimers which are surrounded by polyiodide networks. Moreover, coordination of the pyridinol group to two metal ions transforms the surface charge of the ring from negative to markedly positive, generating a suitable environment for the assembly of polyiodide anions, while N-methylation shifts the directional control of the assembly from H-bonds to I···I interactions. In fact, an extended concatenation of iodine atoms occurs around the complex dimeric cations, the supramolecular I···I interactions become shorter and shorter, fading into stronger forces dominated by the orbital overlap, which is promising for effective electronic materials.

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Section: Results and Discussionmentioning

confidence: 99%

Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

et al. 2021

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“…In both types of chains, the I 3 − anions were asymmetric, with the shorter and longer I–I bond distances being 2.91 and 2.96 Å, respectively, in one chain, and 2.92 and 2.95 Å in another. Despite the slight difference, the average I–I bonding distance fell within the range of 2.92–2.95 Å, typical for I 3 - anions [ 15 , 18 ]. Both I 3 − anions exhibited slight deviations from linearity, the I–I–I angle being 177 deg.…”

Section: Resultsmentioning

confidence: 99%

“…The crystal structure of 2 comprised three building units: the I - and I 3 - anions and the DMPDA dications ( Figure 1 ). The triiodide anion was considerably asymmetric, and the I–I distances were 2.86 and 3.00 Å, which corresponds to the average I–I distance of 2.93 Å, typical for triiodide anions irrespective of their actual symmetry [ 15 , 18 ]. The I 3 − anion was linked to the DMPDA cation through a sole (N)H⋅⋅⋅I interaction of 2.79 Å.…”

Section: Resultsmentioning

confidence: 99%

“…Although the history of polyiodides can be traced back to the 18th century, and many reviews have been published on different topics related to this family of compounds, for example [ 15 , 16 , 17 , 18 ], various aspects of their chemistry remain unknown; most notably, phase relations for low-melting polyiodides of different organic compounds and mechanisms of their transformation into polyiodometallates are poorly investigated [ 2 , 3 , 10 , 12 ]. Some other issues, including intramolecular bonding in polyiodides, require further investigation [ 13 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

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Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative

et al. 2021

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Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2·2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2·I2 and new (DMPDA)2(BiI6)(I3)·2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic–inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋯I and (N)H⋯O hydrogen bonds as well as I⋯I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.

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“…Naturally, any such interaction does not necessarily operate in isolation of other intermolecular forces and may very well cooperate with other obvious supramolecular synthons such as those formed by conventional hydrogen-bonding [5]. With the continuing surge of interest in identifying any number of intermolecular contacts in crystals [6][7][8][9][10], secondary-bonding interactions, including halogen-bonding [11], occupy a prominent position, so much so that a new lexicology has emerged [12][13][14]. Thus, the terms triel- [15], tetrel- [16], pnictogen- [17] and chalcogen-bonding [18] refer to the group the electrophilic element is derived.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

Tiekink

2021

Coordination Chemistry Reviews

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An evaluation of the Cambridge Structural Database for crystals containing Se … N secondary--bonding interactions was conducted. The presence of Se … N secondary-bonding interactions has been established in nearly 9% of crystals of mono-nuclear selenium compounds where such interactions can potentially form, that is, having at least one nitrogen atom. The Se … N interactions feature in 71 zero-dimensional, usually di-nuclear aggregates, 63 one-dimensional chains and tapes, and smaller numbers of two-and three-dimensional arrays, that is seven and one, respectively. Selenium(II) compounds form the majority of the dataset with only eight selenium(IV) compounds included in the survey. In most cases (112 out of 142), the selenium centre forms a single Se … N contact with 26 aggregates having a selenium atom forming two contacts and four examples where three Se … N contacts are evident. The great propensity of selenadiazole rings (75%) and selenocyanates (50%) to form Se … N secondary-bonding interactions in their crystals is particularly noteworthy.

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Words in supramolecular chemistry: the ineffable advances of polyiodide chemistry

Abstract: Foundations of the discording vocabulary of novel supramolecular interactions lay onto polyiodide chemistry. Reviewing advancements in the field, we tackle I⋯I contacts understanding, rationalization, and language on semantic and scientific grounds.

Cited by 38 publications

References 135 publications

Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

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