Influence of Molecular Separation on Through-Space Intervalence Transient Charge Transfer in Metal-Organic Frameworks with Cofacially arranged Redox Pairs.

We demonstrate direct evidence of photoinduced through-space intervalence charge transfer (IVCT) between two cofacially arranged redox-active pairs in metal-organic frameworks and their dynamic variation with their molecular separation. Two homologous MOFs [Co2 (NDC)2 (DPTTZ)2 ]. DPTTZ. DMF, 1 and [Co2 (BDC)2 (DPTTZ)2 ]. DMF, 2 (where NDC=naphthalene dicarboxylate, BDC=benzene dicarboxylate, DPTTZ=N, N'-di(4-pyridyl)thiazolo-[5,4-d]thiazole, DMF=N, N'-dimethyl formamide) are considered for this, whose intra-dimer distance of redox-active DPTTZ ligands differs ca. 1 Šfrom one system to another. Spectroelectrochemical study detects the formation of IVCT band at the NIR region between cofacially oriented DPTTZ molecules in both MOFs. Transient spectroscopy shows faster charge separation as well as charge recombination when intra-dimer distance is lesser (in MOF 2) due to stronger electronic coupling. We quantify the extent of IVCT by charge transfer integral calculation; and also by optical pump terahertz probe spectroscopy, where MOF 2 shows three times higher carrier mobility due to lesser inter-DPTTZ distance than MOF 1. These findings reveal a more localized aspect of through-space IVCT between cofacially organized redox-active pair in a three-dimensional framework.

Mechanistic insight into Pb2+ and Hg2+ ion sensing using cobalt-based coordination polymer in aqueous phase.

Emissive inorganic-organic hybrid materials open up a new prospect of fast and efficient heavy metal ion sensing in an aqueous medium. Here, we demonstrate highly sensitive lead(II) ion detection attributed to excited-state host-guest interaction, where mercury(II) shows lesser quenching efficiency due to both ground- and excited-state interaction.

Inter-Network Charge-Transfer Excited State Formation Within a Two-fold Catenated Metal-Organic Framework.

Charge-transfer excited state (CTES) defines the ability to split photon energy into work producing redox equivalents suitable for photocatalysis. Here, we report inter-net CTES formation within a two-fold catenated crystalline metal-organic framework (MOF), constructed with two linkers, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) and 2,6-dicarboxynaphthalene (NDC). The structural flexibility puts two complementary linkers from two nets in a proximal position to interact strongly. Supported by the electrochemical and steady-state electronic spectroscopic data, this ground-state interaction facilitates forming CTES that can be populated by direct excitation. We map the dynamics of the CTES which persists over a few nanoseconds and highlight the utilities of such relatively long-lived CTES as enhanced conductivity of the MOF under light over that measured in dark and as a proof-of-the-principle test, photo-reduction of methyl viologen under white light.

Revisiting the Dynamics of Triplet Formation in Anthraquinones.

Triplet formation pathways in 9,10-anthraquinone (AQ) and its hydroxy derivative, 1-hydroxyanthraquinone (HAQ), are studied theoretically. Dynamics simulations on the model singlet-triplet potential energy surfaces within the linear vibronic coupling framework are performed to elucidate possible internal conversion (IC) and intersystem crossing (ISC) pathways in these molecules. An ultrafast IC decay from the "bright" S4 to S1 followed by efficient ISC via S1-T4 and S1-T5 pathways fosters a high triplet quantum yield (ΦT = 0.90) in AQ. In HAQ, a new nonradiative channel of "barrierless" excited-state intramolecular proton transfer (ESIPT) opens up and competes with the IC decay to S1 upon photoexcitation to the "bright" S2. Extremely fast ESIPT on S2 reduces the efficiency of triplet formation via possible ISC pathways involving S1 and S2, resulting in a low ΦT (=0.17).

Crystal Packing-Driven Selective Hg(II) Ion Sensing Using Thiazolothiazole-Based Water-Stable Zinc Metal-Organic Framework.

A soft acid-soft base interaction is highly predictable. However, we demonstrate how the crystal packing of the newly synthesized zinc framework [Zn2(5-AIA)2(DPTTZ)]·DMF (where 5-AIA = 5-aminoisophthalic acid, DPTTZ = N,N'-di(4-pyridyl)thiazolo-[5,4-d]thiazole, DMF = N,N'-dimethylformamide) directs an unexpected interaction between the soft acid Hg(II) and the hard base oxygen instead of having a soft center like nitrogen and sulfur in the system attributed to a strong solvent interaction and a favorable ionic radius of Hg(II) ion for oxygen chelation. This engenders selective Hg(II) ion sensing through a "turn-off" emission quenching in water (limit of detection = (2.174 ± 0.06) × 10-9 M) along with natural water resources and in a broad pH range. A quantum-chemical calculation elucidates the turn-off quenching mechanism and favorable Hg(II) interaction with encompassed oxygen atoms inside the framework.

Novel class of water-soluble phosphonate silver cluster assembled material for efficient photoelectric sensing and photoacoustic imaging.

Owing to the atomic precession and exotic photophysical properties, silver cluster assembled materials (CAMs) have been explored for use as functional nanomaterials in recent years. Although a small number of thiolate protected silver CAMs have previously been investigated, the synthesis of thiol-free analogues and their solubility remain challenging. Here, the structure-property correlation of a newly synthesized one-dimensional phenyl phosphonate protected [Ag2(PhPO3H)2(apy)2], (in which, 4,4'-azopyridine = apy) CAM is demonstrated. The multifunctional surface protecting ligand is strategically attached to the core for the first time to tailor the solubility, structural stability and charge transfer mechanism. The small size of the cluster building blocks, along with the choice of organic linker molecules, efficiently stabilize the structure via intra-chain π-π stacking while inter-chains π-π interactions create a two-dimensional supramolecular architecture. The advantageous band structure associated with the charge transfer phenomenon and the high structural stability of the material are guided to explore the sustainable photoresponsive character of this CAM, resulting in the generation of an 82 nA photocurrent. Additionally, the unprecedented water solubility, which is very rare for this class of material, provides opportunities for use in biomedical imaging applications. The measured photoacoustic signal strength confirms the blood vessel mimicking capabilities of the portrayed material at a depth of approximately 3 mm inside chicken breast tissue.

Conductive Metal-Organic Frameworks: Electronic Structure and Electrochemical Applications.

Smarter and minimization of devices are consistently substantial to shape the energy landscape. Significant amounts of endeavours have come forward as promising steps to surmount this formidable challenge. It is undeniable that material scientists were contemplating smarter material beyond purely inorganic or organic materials. To our delight, metal-organic frameworks (MOFs), an inorganic-organic hybrid scaffold with unprecedented tunability and smart functionalities, have recently started their journey as an alternative. In this review, we focus on such propitious potential of MOFs that was untapped over a long time. We cover the synthetic strategies and (or) post-synthetic modifications towards the formation of conductive MOFs and their underlying concepts of charge transfer with structural aspects. We addressed theoretical calculations with the experimental outcomes and spectroelectrochemistry, which will trigger vigorous impetus about intrinsic electronic behaviour of the conductive frameworks. Finally, we discussed electrocatalysts and energy storage devices stemming from conductive MOFs to meet energy demand in the near future.

Reversible polymorphic structural transition of crown-like nickel nanoclusters and its effect on conductivity.

We report the reversible polymorphic phase transition of [Ni6(PET)12] (PET = phenylethanethiol) and its effect on the conductivity. This cluster's self-assembly leads to two polymorphic structures with distinct conductivity, caused by variation of the non-covalent SS interactions. These results enlighten the effect of non-covalent interactions on conductivity.