Binding Modes of Salicylic Acids to Titanium Oxide Molecular Surfaces

Liu, Caiyun; Hu, Jie; Liu, Weiming; Zhu, Feng; Guo, Wei; Tung, Chen‐Ho; Wang, Yifeng

doi:10.1002/chem.201904302

Cited by 27 publications

(25 citation statements)

References 47 publications

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“…13−17 However, despite these efforts for achieving a wide range of colorful TOCs, an optical band gap low enough to allow the absorption of the full visible spectrum had so far not been achieved. [13][14][15]18 Additionally, a large number of known TOCs are synthesized using conventional solvents including alcohols or acetonitrile, making them quite sensitive to moisture. [13][14][15]19 Possibly due to these adverse factors, to the best of our knowledge, there has so far been no homometallic TOC material to show effective third-order NLO behavior.…”

Section: ■ Introductionmentioning

confidence: 99%

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance

Gao

Wang

et al. 2022

J. Am. Chem. Soc.

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A series of catecholate-functionalized titanium-oxo clusters (TOCs), PTC-271 to PTC-277, with atomically precise structures were synthesized and characterized, including distinctive "boat" and "chair" conformations in PTC-273 and PTC-274, respectively. These cluster compounds are prominent for their ultralow optical band gaps, as is visually evident from the rather unusual black TOCs (B-TOCs), PTC-272 to PTC-277. The cluster structures were found to be ultrastable with respect to air, water, organic solvents, and even acidic or basic aqueous solutions in a wide pH range (pH 0−13), owing to the stabilizing effects of catecholate and its derivatives, as well as the carboxylate ligands. Another prominent feature is the occurrence of thirdorder nonlinear optical (NLO) performance, which has previously been unreported in the field of homometallic titanium-oxo clusters. Open-aperture Z-scan experiments show significant solid-state optical limiting (OL) applications of these B-TOCs, with high laser irradiation stability and low minimum normalized transmittance (T min ) of PTC-273 as ∼0.17. Meanwhile, theoretical calculations indicate that the smaller band gaps of B-TOCs were beneficial for strengthening the NLO response. This work not only represents a significant milestone in the construction of stable low-band gap black titanium oxide materials but also contributes to the mechanism insights into their optical applications.

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Section: ■ Introductionmentioning

confidence: 99%

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance

Gao

Wang

et al. 2022

J. Am. Chem. Soc.

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“…In research into dye‐sensitized solar cells (DSSCs) and photocatalysis, the surface structure of TiO 2 nanocrystals and the binding modes of organic sensitizers/adsorbents are critical to photon absorption, electronic excitation, charge transfer (CT), and subsequent surface chemical reactions [37] . However, detailed diffraction information on the structure of the these systems is not available.…”

Section: Postfunctionalization Of Tocsmentioning

confidence: 99%

Supramolecular Chemistry of Titanium Oxide Clusters

Liu

Wang

2021

Chemistry A European J

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Titanium oxide clusters (TOCs) have been emerging as a new type of inorganic molecular entities of supramolecular chemistry. Herein, a perspective on the structures and functionalities of TOCs over the past three decades is given and the paramount roles of TOCs in serving supramolecular chemistry are demonstrated. Four types of supramolecular assemblies based on TOCs are reviewed, namely, TOC hosts for ion inclusion, mechanically interlocked molecular systems built from cyclic TOCs, reactivities of surface sites toward ligand exchange, and hierarchical structures of TOCs. The principles and advantages of TOCs toward each application are fully discussed, along with structural analyses. Following this path, more functional TOC‐based supramolecular systems may be designed and synthesized in the future, which, in turn, will certainly enhance research into both supramolecular and coordination chemistry of titanium.

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“…Note that only representative MOFs based on group 3 and 4 metals (excluding Sc and Hf) since 2018 and previous MOF milestones are listed; b) Linkers are abbreviated as: ABTC = 3,3′,5,5′-azobenzene-tetracarboxylate; AZDC = azobenzene-3,3′-dicarboxylate; ATDB = 4,4′-(4-amino-4H-1,2,4-triazole-3,5-diyl)-dibenzoate; ATPC = 4′,4′′,4′′′,4′′′′-(anthracene-9,10-diylidenebis(methan-1,1-diyl-1-ylidene))tetrabiphenyl-4-carboxylate; ATBC = 4,4′,4′′,4′′′-(anthracene-9,10-diylidenebis(methan-1,1-diyl-1-ylidene)) tetrabenzoate; BDC = terephthalate; BTTC = benzotristhiophene carboxylate; BHPB = hexakis(4-(4-carboxyphenyl)phenyl)benzoate; BDHA = benzene-1,4-dihydroxamic acid; BDB = 4,4′-(benzene-1,3-diyl)dibenzoate; BTDB = 4,4′-(benzo[c] [1,2,5]thiadiazole-4,7-diyl)dibenzoate; BTBA = 4,4′,4′′-(1H-benzo-[d]imidazole-2,4,7-triyl)tribenzoate; BPDC = biphenyl-4,4′-dicarboxylate; BPyDC = 2,2′-bipyridyl-5,5′-dicarboxylate; BTB = 1,3,5-benzenetrisbenzoate; CPTPY = 4′-(4-carboxyphenyl)-terpyridine; BTB = benzene tribenzoate; CBTB = 4,4′,4′′,4′′′-(9H-carbazole-1,3,6,8-tetrayl)tetrabenzoate; DCDPS = 4,4′-dicarboxydiphenyl sulfone; DTPP = 5,15-di(3,4,5-trihydroxyphenyl)porphyrin; DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid; EDDB = 4,4′-(ethyne-1,2-diyl)dibenzoate; FUM = fumarate; 2,6-NDC = naphthalene-2,6-dicarboxylate; HBCPB = 1,2,3,4,5,6-hexakis[3,5-bis(4-carboxyphenyl)phenoxymethyl]benzene; HCHC = hexakis(4-carboxyphenyl)hexabenzocoronene; H 6 CPB/HCBB = 1′,2′,3′,4′,5′,6′-hexakis(4carboxyphenyl)benzene; H 6 TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid; H 2 DHBQ = 2,5-dihydroxybenzoquinone; INA = isonicotinate; L-AA = L-Aspartic acid; MDIP = 3,3′,5,5′-tetracarboxydiphenylmethane; PDC = 2,5-pyridinedicarboxylate; P-2COOH = N,N′-di-(4-benzoic acid)-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide; TCPP = meso-tetrakis(4-carboxylatephenyl)porphyrin; TTFTB = tetrathiafulvalene-tetrabenzoate; TDHT = 2,4,6-tri(3,4-dihydroxyphenyl)-1,3,5triazine; TCPC = 5,10,15-tris(p-carboxylphenyl)corrole; TBAPY = 1,3,6,8-tetrakis(p-benzoic acid)pyrene; TTFTB = tetrathiafulvalene tetrabenzoate; TPHB = 4,4′,4′′,4′′′,4′′′′,4′′′′-(triphenylene-2,3,6,7,10,11-hexayl)hexabenzoate; THPP = 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin); THBPP = 5,10,15,20-tetrakis(3,4,5-trihydroxybiphenyl)porphyrin; TPDC = 2′,5′-dimethyl-terphenyl-4,4′′-dicarboxylate; TTDA = 5′-(1H-tetrazol-5-yl)-1,1′:3′,1′′-terphenyl-4,4′′-dicarboxylate; TBCPB = 1,2,4,5-tetrakis [ Ti-oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments. [48] The number of Ti atoms in Ti-oxo clusters ranges from 3 to 32, including Ti 3 , [49][50][51][52] Ti 4 , [50,[52][53][54][55][56][57] Ti 5 , [57] Ti 6 ,…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

“…Ti–oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments. [ 48 ] The number of Ti atoms in Ti–oxo clusters ranges from 3 to 32, including Ti 3 , [ 49–52 ] Ti 4 , [ 50,52–57 ] Ti 5 , [ 57 ] Ti 6 , [ 51,52,54,55,57–64 ] Ti 7 , [ 57 ] Ti 8 , [ 54,64,65 ] Ti 9 , [ 51,55,63 ] Ti 10 , [ 66 ] Ti 11 , [ 54–56,63 ] Ti 12 , [ 57,62,66,67 ] Ti 14 , [ 50,56 ] Ti 16 , [ 54,55,61,66 ] Ti 18 , [ 51,57 ] Ti 19 , [ 63 ] Ti 20 , [ 66,68 ] and Ti 32 clusters. [ 69 ] In general, during the assembly of Ti–oxo clusters, it is vital to control the competition between acids and coordinating ligands.…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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Binding Modes of Salicylic Acids to Titanium Oxide Molecular Surfaces

Cited by 27 publications

References 47 publications

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance

Supramolecular Chemistry of Titanium Oxide Clusters

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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