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Metal halide perovskite ferroelectrics combining spontaneous polarization and excellent semiconducting properties is an ideal platform for enabling self-driven X-ray detection. However, achievements to date have been only based on uniaxiality, which increases the complexity of device fabrication. Multi-axial ferroelectric materials have multiple equivalent polarization directions, making them potentially amenable to multi-axial self-driven X-ray detection, but the report on these types of materials is still a huge blank. Herein, a high-quality (BA) 2 (EA) 2 Pb 3 I 10 (1) biaxial ferroelectric single crystal was successfully grown, which exhibited significant spontaneous polarization along the c-axis and b-axis. Under X-ray irradiation, bulk photovoltaic effect (BPVE) was exhibited along both the c-axis and b-axis, with open circuit voltages (V oc ) of 0.23 V and 0.22 V, respectively. Then, the BPVE revealed along the inversion of polarized direction with the polarized electric fields. Intriguingly, due to the BPVE of 1, 1 achieved multi-axial self-driven X-ray detection for the first time (c-axis and b-axis) with relatively high sensitivities and ultralow detection limits (17.2 nGy air  s -1 and 19.4 nGy air  s -1 , respectively). This work provides a reference for the subsequent use of multi-axial ferroelectricity for multi-axial self-driven optoelectronic detection., (© 2024 Wiley-VCH GmbH.)

In this research, indium ions were introduced into polyoxoniobates (PONbs) reaction systems to facilitate the construction of different {SiNb 18 O 54 }-based aggregates, including an {In(en) 2 {SiNb 18 O 54 } 2 } (en = ethylenediamine) dimer, an {[InO 2 ][In 2 (en)O 3 ] 2 {SiNb 18 O 54 } 3 } trimer, and an {[In(en) 2 ][InO 2 ][In 7 (en) 5 O 9 ]{SiNb 18 O 54 } 4 } tetramer. Interestingly, these aggregates were further assembled into three uncommon extended PONb architectures in the presence of [Cu(en) 2 ] 2+ complexes, namely, H 3 [Cu(en) 2 (H 2 O)][Cu(en) 2 ] 6 [Cu(en) 2 ] 2 {[In(en) 2 ][K 2 {SiNb 18 O 54 }(H 2 O) 6 ] 2 }·1.5en·16H 2 O, H 9 {[Cu(en) 2 ] 6 {[Cu(en) 2 ] 3 [Cu(en) 2 (H 2 O)][In(H 2 O) 2 ][In 2 (en)(H 2 O) 2 (OH)] 2 {SiNb 18 O 54 } 3 }·5en·29H 2 O, and H 14 [Cu(en) 2 ] 0.5 [Cu(en) 2 (H 2 O)]{[Cu(en) 2 ] 2 {[Cu(en) 2 ] 3 [Cu(en) 2 (H 2 O)] 5 [K(H 2 O) 2 ][In(H 2 O) 2 ][In(en) 2 ][In 7 (OH) 9 (en) 5 ]{SiNb 18 O 54 } 4 }·7en·39H 2 O. In addition, all of them have good water vapor adsorption capacities and moderate proton transport capabilities. The above results indicate that introducing suitable heteroatoms to induce the aggregation PONb building blocks and further assembling them into new structures is an effective strategy to enrich the PONbs' structural diversity and develop new functional materials.

Photopyroelectric-based circularly polarized light (CPL) detection, coupling the pyro-phototronic effect and chiroptical phenomena, has provided a promising platform for high-performance CPL detectors. However, as a novel detection strategy, photopyroelectric-based CPL detection is currently restricted by the short-wave optical response, underscoring the urgent need to extend its response range. Herein, visible-to-near-infrared CPL detection induced by the pyro-phototronic effect is first realized in chiral-polar perovskites. Specifically, chiral-polar multilayered perovskites (S-BPEA) 2 FAPb 2 I 7 (1-S, S-BPEA = (S)-1-4-Bromophenylethylammonium, FA = formamidinium) with spontaneous polarization shows intrinsic pyroelectric and photopyroelectric performance. Strikingly, combining its merits of the pyro-phototronic effect and intrinsic wide-spectrum spin-selective effect, chiral multilayered 1-S presents efficient photopyroelectric-based broadband CPL detection performance spanning 405-785 nm. This research first realizes photopyroelectric-based infrared CPL detection and also sheds light on developing high-performance broadband CPL detectors based on the pyro-phototronic effect in the fields of optics, optoelectronics, and spintronics., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

2D organic-inorganic hybrid perovskites (OIHPs) have shown great promise in direct X-ray detection. The development of high-performance passive X-ray detectors in 2D OIHPs calls for an increase in material density while maintaining structural polarity, which is becoming quite challenging. Here, a high-density, polar 2D alternating-cation-intercalated (ACI) perovskite, (4-AP)Cs 2 Pb 2 I 8 ( B , 4-AP = 4-amidinopyridinium), capable of addressing this problem is successfully constructed by introducing heavy Cs + into the interlayer space of an aromatic Dion-Jacobson (DJ) perovskite (4-AP)PbI 4 ( A ). Through such a DJ-to-ACI design, the newly developed 2D OIHP B not only significantly increases its density to 4.23 g cm -3 (even higher than that of 3D MAPbI 3 ) but also crystallizes in a polar space group ( Ama 2), which further leads to enhanced X-ray attenuation and an obvious polar photovoltage (1.1 V) under X-ray irradiation. As a result, X-ray detectors fabricated by high-quality single crystals of B exhibit excellent and stable detection performance under self-powered mode with a high sensitivity of 107 μC Gy -1 cm -2 and a low detection limit of 289 nGy s -1 . This work provides implications for the future exploration and regulation of novel ACI OIHPs for high-performance photoelectronic devices.

The low-toxic and environmentally friendly 2D lead-free perovskite has made significant progress in the exploration of "green" X-ray detectors. However, the gap in detection performance between them and their lead-based analogues remains a matter of concern that cannot be ignored. To reduce this gap, shortening the interlayer spacing to accelerate the migration and collection of X-ray carriers is a promising strategy. Herein, a Dion-Jacobson (DJ) lead-free double perovskite (4-AP) 2 AgBiBr 8 (1, 4-AP = 4-amidinopyridine) with an ultra-narrow interlayer spacing of 3.0 Å, is constructed by utilizing π-conjugated aromatic spacers. Strikingly, the subsequent enhanced carrier transport and increased crystal density lead to X-ray detectors based on bulk single crystals of 1 with a high sensitivity of 1117.3 µC Gy -1  cm -2 , superior to the vast majority of similar double perovskites. In particular, the tight connection of the inorganic layers by the divalent cations enhances structural rigidity and stability, further endowing 1 detector with ultralow dark current drift (3.06 × 10 -8  nA cm -1  s -1  V -1 , 80 V), excellent multiple cycles switching X-ray irradiation stability, as well as long-term environmental stability (maintains over 94% photoresponse after 90 days). This work brings lead-free double perovskites one step closer to realizing efficient practical green applications., (© 2024 Wiley‐VCH GmbH.)

Metal halide perovskites have outperformed conventional inorganic semiconductors in direct X-ray detection due to their ease of synthesis and intriguing photoelectric properties. However, the operational instability caused by severe ion migration under a high external electric field is still a big concern for the practical application of perovskite detectors. Here, we report a 2D (BPEA) 2 PbI 4 (BPEA = R -1-(4-bromophenyl)ethylammonium) perovskite with Br-substituted aromatic spacer capable of introducing abundant interactions, e.g., the molecular electrostatic forces between Br atoms and aromatic rings and halogen bonds of Br-I, in the interlayer space, which effectively suppresses ion migration and thus enables superior operational stability. Constructing direct X-ray detectors based on high-quality single crystals of (BPEA) 2 PbI 4 results in a high sensitivity of 1,003 μC Gy -1 cm -2 , a low detection limit of 366 nGy s -1 , and an ultralow baseline drift of 3.48 × 10 -8 nA cm -1 s -1 V -1 at 80 V bias. More strikingly, it also exhibits exceptional operational stability under high flux, long-time X-ray irradiation, and large working voltage. This work shows an integration of multiple interlayer interactions to stabilize perovskite X-ray detectors, providing new insights into the future design of perovskite optoelectronic devices toward practical application., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Polar photovoltaic effect (PPE) has attracted great attention in regulating desired optoelectronic properties, which can be driven by order-disorder and displacive phase transitions. Bond-switching is also a feasible method to induce PPE, but such investigation is very rare. Lead-halide hybrid perovskite (LHHP) is an outstanding photodetection material; lead atoms possess rich coordination modes to provide possibilities to construct switchable bonds. Here, a unique perovskitizer N─Pb bond-switching is disclosed to induce polar photovoltage in the emerging LHHP, PA 2 MHy 2 Pb 3 Br 10 (1, PA = n-propylamine, MHy = methylhydrazine). Interestingly, the perovskitizer MHy + provides 2s 2 lone pair while the Pb atom affords empty d orbitals, which coordinate with each other to generate a flexible N─Pb bond. Further, the introduction of N─Pb bonds results in a high distortion of the PbBr 6 octahedron to form local polarity and further orientation to induce spontaneous polarization. More importantly, such a flexible N─Pb bond switching mechanism drives a notable PPE and controllable polarized photo-response, a polarization ratio up to 9.7 at the polar phase in striking contrast with the non-polar phase (1.03). The work provides the first demonstration of bond-switching to induce polar phase transition and polar photovoltage in the photoconductive hybrid perovskites for photoelectric applications., (© 2023 Wiley‐VCH GmbH.)

Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) have achieved tremendous success in direct X-ray detection due to their high absorption coefficient and excellent carrier transport. However, owing to the centrosymmetry of classic 3D structures, these reported X-ray detectors mostly require external electrical fields to run, resulting in bulky overall circuitry, high energy consumption, and operational instability. Herein, we first report the unprecedented radiation photovoltage in 3D OIHP for efficient self-driven X-ray detection. Specifically, the 3D polar OIHP MhyPbBr 3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47 V) and large mobility-lifetime product (1.1×10 -3  cm 2  V -1 ) under X-ray irradiation. Strikingly, these excellent physical characteristics endow 1 with sensitive self-driven X-ray detection performance, showing a considerable sensitivity of 220 μC Gy -1  cm -2 , which surpasses those of most self-driven X-ray detectors. This work first explores highly sensitive self-driven X-ray detection in 3D polar OIHPs, shedding light on future practical applications., (© 2024 Wiley-VCH GmbH.)

2D multilayered organic-inorganic hybrid perovskites (OIHPs) have exhibited bright prospects for high-performance self-driven X-ray detection due to their strong radiation absorption and long carrier transport. However, as an effective tool for self-driven X-ray detection, radiation photovoltaics remain rare, and underdeveloped in multilayered OIHPs. Herein, chirality to induce radiation photovoltaics in 2D multilayered chiral OIHPs is first utilized for efficient self-driven X-ray detection. Specifically, under X-ray irradiation, a multilayered chiral-polar (S-BPEA) 2 FAPb 2 I 7 (1-S, S-BPEA = (S)-1-4-Bromophenylethylammonium, FA = formamidinium) shows remarkable radiation photovoltaics of 0.85 V, which endows 1-S excellent self-driven X-ray detection performance with a considerable sensitivity of 87.8 µC Gy air -1  cm -2 and a detection limit low to 161 nGy air  s -1 . Moreover, the sensitivity is high up to 1985.9 µC Gy air -1  cm -2 under 80 V bias, higher than most those of 2D OIHPs. These results demonstrate that chirality-induced radiation photovoltaics is an efficient strategy for self-driven X-ray detection., (© 2023 Wiley‐VCH GmbH.)

Lead halide hybrid perovskites have made great progress in direct X-ray detection and broadband photodetection, but the existence of toxic Pb and the demand for external operating voltage have severely limited their further applications and operational stability improvements. Therefore, exploring "green" lead-free hybrid perovskite that can both achieve X-ray detection and broadband photodetection without external voltage is of great importance, but remains severely challenging. Herein, using centrosymmetric (BZA) 3 BiI 6 (1, BZA = benzylamine) as a template, a pair of chiral-polar lead-free perovskites, (BZA) 2 (R/S-PPA)BiI 6 (2-R/S, R/S-PPA = (R/S)-1-Phenylpropylamine) are successfully obtained by introducing chiral aryl cations of (R/S)-1-Phenylpropylamine. Compared to 1, chiral-polar 2-R presents a significant irradiation-responsive bulk photovoltaic effect (BPVE) with an open circuit photovoltage of 0.4 V, which enables it with self-powered X-ray, UV-vis-NIR broadband photodetection. Specifically, 2-R device exhibits an ultralow detection limit of 18.5 nGy s -1 and excellent operational stability. Furthermore, 2-R as the first lead-free perovskite achieves significant broad-spectrum (377-940 nm) photodetection via light-induced pyroelectric effect. This work sheds light on the rational crystal reconstruction engineering and design of "green" hybrid perovskite toward high-demanded self-powered radiation detection and broadband photodetection., (© 2023 Wiley‐VCH GmbH.)

Circularly polarized light (CPL) detection has wide applications in many fields, where the anisotropy factor (g Iph ) is an important indicator to characterize the CPL detection performance. So far, many materials with high g Iph have been reported, however, the exploration of the regulation of g Iph is still in its infancy. Herein, two novel alternating chiral-achiral cations intercalation-type chiral hybrid perovskites (CHPs), named (R/S-1-phenylpropylamine)(propylamine)PbBr 4 (1-R/S), exhibit above room-temperature (RT) polar-phase transition, which greatly regulates the g Iph value. The g Iph of 1-R is 0.04 in high-temperature phase chiral non-polar (P2 1 2 1 2 1 ) by applying 5 V bias, interestingly, with the temperature decrease, the g Iph value in low-temperature phase chiral polar (P2 1 ) gradually increases (0.22@360K, 0.40@340K, 0.47@320K), and finally reaches a maximum of 0.5 at RT. Such value is not only the highest among 2D CHPs to date, but presents a 12.5-fold amplification compared with 0.04. Further, this rare phenomenon should be attributed to the built-in electric field induced by the polar photovoltaic effect, which sheds light on further obtaining CHPs with large g Iph ., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Chiral hybrid perovskites combine the advantages of chiral materials and halide perovskites, offering an ideal platform for the design of circularly polarized light (CPL) detectors. The pyro-phototronic effect, as a special mechanism of the photoexcited pyroelectric signal, can significantly improve the performance of photodetectors, whereas it remains a great challenge to achieve pyroelectricity-based CPL detection. In this work, the chiroptical phenomena and the pyro-phototronic effect are combined in chiral-polar perovskites to achieve unprecedented pyroelectric-based CPL detection. Two novel two-dimensional (2D) lead-free chiral-polar double perovskites, S / R -[(4-aminophenyl)ethylamine] 2 AgBiI 8 ·0.5H 2 O, are successfully designed and synthesized by introducing chiral organic ligands into metal halide frameworks. Strikingly, the photoresponse is substantially boosted with the support of the pyro-phototronic effect, showing an increased pyro-phototronic current that is 40 times greater than the photovoltaic current. Furthermore, the pyroelectric-based detector possesses excellent CPL detection capacity to distinguish different polarization states of CPL photons, which achieve an impressive g lph of up to 0.27 at zero bias. This study provides a brand new process for CPL detection by utilizing the pyro-phototronic effect in chiral-polar perovskites, which opens a new avenue for chiral materials in optoelectronic applications.

The intrinsic integration of structural flexibility, chiroptical activity, and photoelectric properties endows the two-dimensional (2D) chiral hybrid perovskites (CHPs) with significant application potential in chiroptoelectronics and spintronics. However, the scarcity of suitable chiral organic ligands severely hinders their extensive construction, necessitating the development of new strategies for designing 2D CHPs. Herein, by exploiting a half substitution method, we created a pair of 2D CHPs with alternating cations in the interlayer space (ACI), ( R / S -PPA)(PA)PbBr 4 (2 R /2 S , PPA = 1-phenylpropylamine, PA = n -pentylamine), from the achiral Ruddlesden-Popper (RP) (PA) 2 PbBr 4 (1). The successful chirality transfer induces 2 R /2 S to crystallize in the chiral P 2 1 2 1 2 1 space group and thus acquire appealing chiroptical activity. Consequently, the single-crystal devices of 2 R exhibit good distinguishability to the left- and right-handed circularly polarized 405 nm lights with a photocurrent dissymmetric factor of 0.10 at 10 V bias. This work demonstrates an intriguing achiral RP to chiral ACI motif reconstruction in 2D halide hybrid perovskites, opening a door for expanding the family of 2D CHPs.

Chiral three-dimensional hybrid organic-inorganic perovskites (3D HOIPs) would show unique chiroptoelectronic performance due to the combination of chirality and 3D structure. However, the synthesis of 3D chiral HOIPs remains a significant challenge. Herein, we constructed a pair of unprecedented 3D chiral halide perovskitoids (R/S-BPEA)EA 6 Pb 4 Cl 15 (1-R/S) (R/S-BPEA=(R/S)-1-4-Bromophenylethylammonium, EA=ethylammonium), in which the large chiral cations can be contained in the big "hollow" inorganic frameworks induced by mixing cations. Notably, 3D 1-R/S shows natural chiroptical activity, as evidenced by its significant mirror circular dichroism spectra and the ability to distinguish circularly polarized light. Moreover, based on the unique 3D structure, 1-S presents sensitive X-ray detection performance with a low detection limit of 398 nGy air  s -1 , which is 14 times lower than the regular medical diagnosis of 5.5 μGy air  s -1 . In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics., (© 2023 Wiley-VCH GmbH.)

Chiral perovskites have been demonstrated as promising candidates for direct circularly polarized light (CPL) detection due to their intrinsic chirality and excellent charge transport ability. However, chiral perovskite-based CPL detectors with both high distinguishability of left- and right-handed optical signals and low detection limit remain unexplored. Here, a heterostructure, (R-MPA) 2 MAPb 2 I 7 /Si (MPA = methylphenethylamine, MA = methylammonium) is constructed, to achieve high-sensitive and low-limit CPL detection. The heterostructures with high crystalline quality and sharp interface exhibit a strong built-in electric field and a suppressed dark current, not only improving the separation and transport of the photogenerated carriers but also laying a foundation for weak CPL signals detection. Consequently, the heterostructure-based CPL detector obtains a high anisotropy factor up to 0.34 with a remarkably low CPL detection limit of 890 nW cm -2 under the self-driven mode. As a pioneering study, this work paves the way for designing high-sensitive CPL detectors that simultaneously have great distinguishing capability and low detection limit of CPL., (© 2023 Wiley-VCH GmbH.)

Broadband photodetectors (PDs) with low detection limits hold significant importance to next-generation optoelectronic devices. However, simultaneously detecting broadband (i.e., X-ray to visible regimes) and weak lights in a single semiconducting material remains highly challenging. Here, by alloying iodine-substituted short-chain cations into the 3D FAPbI 3 (FA = formamidine), a new 2D bilayered lead iodide hybrid perovskite, (2IPA) 2 FAPb 2 I 7 (1, 2IPA = 2-iodopropylammonium), that enables addressing this challenge is reported. Such a 2D multilayered structure and lead iodide composition jointly endow 1 with a minimized dark current (6.04 pA), excellent electrical property, and narrow bandgap (2.03 eV), which further gives it great potential for detecting broadband weak lights. Consequently, its high-quality single crystal PDs exhibit remarkable photoresponses to weak ultraviolet-visible lights (377-637 nm) at several tens of nW cm -2 with high responsivities (>10 2  mA W -1 ) and significant detectivities (>10 12 Jones). Moreover, 1 has an excellent X-ray detection performance with a high sensitivity of 438 µC Gy -1 cm -2 and an ultralow detection limit of 20 nGy s -1 . These exceptional attributes make 1 a promising material for broadband weak lights detection, which also sheds light on future explorations of high-performance PDs based on 2D hybrid perovskites., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Two new extended polyoxometalate (POM) architectures based on lanthanide-incorporated polyoxoniobate (Ln-incorporated PONb) cages, namely, H 4 [Cu II (en) 2 ] 4 {K 4 (H 2 O) 2 [Cu II (en) 2 ] 5 [Cu II 5 (trz) 2 (en) 4 (OH) 2 ][Dy 2 Cu II 2 (en) 2 (CO 3 ) 3 (H 2 O) 2 (OH) 3 ][Dy(H 2 O) 4 ][DyNb 23 O 68 (H 2 O) 4 ] 2 }·60H 2 O ( 1 , en = ethylenediamine) and H 20 [Cu II (en) 2 ] 4 {[Cu II (en) 2 ] 4 [Dy 2 (C 2 O 4 )(H 2 O) 4 ] 2 [(Nb 32 (OH) 4 (H 2 O) 3 O 89 ] 2 }·54H 2 O ( 2 ), have been successfully synthesized and structurally characterized, demonstrating a feasible strategy to develop functional POM materials. In addition, the proton conductivity and magnetic behaviors of both 1 and 2 were studied.

Cup-shaped molecules are of great interest due to their appealing architectures and properties. Compared with widely studied calixarenes, polyoxometalate-based cup-shaped molecules currently remain a virgin land waiting for exploration. In this work, we report the first discovery of two giant cup-shaped inorganic-organic hybrid polyoxoniobates (PONbs) of {Cu 12 Nb 120 } and {Cd 16 Nb 128 }. The former integrates three tricyclic Nb 24 clusters and a hexacyclic Nb 48 cluster into a cup-shaped molecule via a Cu 12 metallacalixarene, while the latter unifies two tricyclic Nb 24 clusters and a brand-new pentacyclic Nb 40 cluster into another cup-shaped molecule via a hybrid Cd 16 unit. With 132 and 144 metal centers, {Cu 12 Nb 120 } and {Cd 16 Nb 128 } show the largest two inorganic-organic hybrid PONbs known to date., (© 2021 Wiley-VCH GmbH.)

Nanoscale {Nb68O200} cages have been successfully employed as flexible and stable secondary building units to combine with bridging copper-amine complexes to construct two proton conductive polyoxoniobate frameworks, demonstrating a promising strategy for making new porous materials.

A rare 3D porous inorganic-organic polyoxoniobate framework based on the cubic polyoxoniobate-cupric-complex cage {[Cu(en) 2 ]@{[Cu 2 (en) 2 (trz) 2 ] 6 (Nb 68 O 188 )}} ( 1a ), has been successfully synthesized by a hydrothermal method. The cubic cages 1a are connected with 4-(tetrazol-5-yl)pyridine to form a 1D pillar-like chain structure, and every 1D pillar-like chain is further linked with four adjacent pillar-like chains by the [Cu(en) 2 ] 2+ complex to form a 3D porous inorganic-organic polyoxoniobate framework with 4-connected CdSO 4 -type topology. To our knowledge, it is the first time that three different types of organic ligands are simultaneously introduced into one polyoxoniobate. This material also exhibits a high vapor adsorption capacity and good ionic conductivity properties.

In this work, two rare high-dimensional polyoxoniobates with formulas of H 9 [Cu(en)(H 2 O) 2 ][Cu(en) 2 ] 8 [Dy(H 2 O) 4 ] 3 [Nb 24 -O 69 (H 2 O) 3 ] 2  ⋅ 36H 2 O (1) and H 9 K[Cu(en) 2 (H 2 O)] 5 [Cu(en) 2 ] 4 -[Eu(H 2 O) 4 ] 3 [Nb 24 O 69 (H 2 O) 3 ] 2  ⋅ 2en ⋅ 45H 2 O (2) have been obtained under hydrothermal conditions. These extended materials are constructed from lanthanide-incorporated triangular-prism-like polyoxoniobate secondary building units (SBUs) {[Ln(H 2 O) 4 ] 3 [Nb 24 O 69 (H 2 O) 3 ] 2 } (Ln=Dy, Eu). 1 and 2 represent the first examples of high-dimensional polyoxometalate materials based on such lanthanide-incorporated triangular-prism-like polyoxoniobate SBUs. Furthermore, the proton conduction property and the luminescent emission of these materials were evaluated., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K 4 @{[Cu 29 (OH) 7 (H 2 O) 2 (en) 8 (trz) 21 ][Nb 24 O 67 (OH) 2 (H 2 O) 3 ] 4 } and [Cu(en) 2 ]@{[Cu 2 (en) 2 (trz) 2 ] 6 (Nb 68 O 188 )} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic-organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage-based extended assembly to form a 3D cage framework {[Cu(en) 2 ]@{[Cu 2 (trz) 2 (en) 2 ] 6 [H 10 Nb 68 O 188 ]}}. These materials exhibit visible-light-driven photocatalytic H 2 evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic-organic hybrid PONb chemistry., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series containing the highest nuclearity polyoxoniobate (PONb) nanoclusters, ranging from dimers to tetramers, has been obtained. They include one 114-nuclear {Li 8 ⊂Nb 114 O 316 }, one 81-nuclear {Li 3 K⊂Nb 81 O 225 }, and one 52-nuclear {H 4 Nb 52 O 150 }. The Nb nuclearity of these PONbs is remarkably larger than those of all known high-nuclearity PONbs (≤32). Furthermore, the introduction of 3d Cu 2+ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H 3 Cu 3 Nb 78 O 222 } or {H 3 Cu 4 (en)Nb 78 O 222 }. These building blocks also contain the largest number of Nb centers of any heterometallic PONbs reported to date. The synthesis of new-type PONbs has long been a challenging subject in PONb chemistry., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)