Dion-Jacobson Type Lead-Free Double Perovskite with Ultra-Narrow Aromatic Interlayer Spacing for Highly Sensitive and Stable X-ray Detection.

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 AgBiBr8 (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.

Three-Dimensional Polar Perovskites for Highly Sensitive Self-Driven X-Ray Detection.

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 MhyPbBr3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47 V) and large mobility-lifetime product (1.1×10-3  cm2 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.

Regulating Circularly Polarized Light Detection via Polar-Phase Transition in Alternating Chiral-Achiral Cations Intercalation-Type Hybrid Perovskites.

Circularly polarized light (CPL) detection has wide applications in many fields, where the anisotropy factor (gIph ) is an important indicator to characterize the CPL detection performance. So far, many materials with high gIph have been reported, however, the exploration of the regulation of gIph is still in its infancy. Herein, two novel alternating chiral-achiral cations intercalation-type chiral hybrid perovskites (CHPs), named (R/S-1-phenylpropylamine)(propylamine)PbBr4 (1-R/S), exhibit above room-temperature (RT) polar-phase transition, which greatly regulates the gIph value. The gIph of 1-R is 0.04 in high-temperature phase chiral non-polar (P21 21 21 ) by applying 5 V bias, interestingly, with the temperature decrease, the gIph value in low-temperature phase chiral polar (P21 ) 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 gIph .

Chiral-Achiral Cations Intercalation Induced Lead-Free Chiral-Polar Hybrid Perovskites Enable Self-Powered X-Ray and Ultraviolet-Visible-Near-Infrared Photo Detection.

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 BiI6 (1, BZA = benzylamine) as a template, a pair of chiral-polar lead-free perovskites, (BZA)2 (R/S-PPA)BiI6 (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.

Circularly Polarized Light-Dependent Pyro-Phototronic Effect from 2D Chiral-Polar Double Perovskites.

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]2AgBiI8·0.5H2O, 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 glph 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.

Unique Perovskitizer N─Pb Bond Switching Induced Polar Photovoltaic Effect in Trilayered Hybrid Perovskite.

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, PA2 MHy2 Pb3 Br10 (1, PA = n-propylamine, MHy = methylhydrazine). Interestingly, the perovskitizer MHy+ provides 2s2 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 PbBr6 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.

Radiation Photovoltaics in a 2D Multilayered Chiral-Polar Halide Perovskite toward Efficient Self-Driven X-Ray Detection.

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 FAPb2 I7 (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 Gyair -1  cm-2 and a detection limit low to 161 nGyair  s-1 . Moreover, the sensitivity is high up to 1985.9 µC Gyair -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.

Alternating chiral and achiral spacers for constructing two-dimensional chiral hybrid perovskites toward circular-polarization-sensitive photodetection.

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)PbBr4 (2R/2S, PPA = 1-phenylpropylamine, PA = n-pentylamine), from the achiral Ruddlesden-Popper (RP) (PA)2PbBr4 (1). The successful chirality transfer induces 2R/2S to crystallize in the chiral P212121 space group and thus acquire appealing chiroptical activity. Consequently, the single-crystal devices of 2R 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.

Unprecedented Chiral Three-dimensional Hybrid Organic-Inorganic Perovskitoids.

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)EA6 Pb4 Cl15 (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 nGyair s-1 , which is 14 times lower than the regular medical diagnosis of 5.5 µGyair s-1 . In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics.

Weak X-Ray to Visible Lights Detection Enabled by a 2D Multilayered Lead Iodide Perovskite with Iodine-Substituted Spacer.

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 FAPbI3 (FA = formamidine), a new 2D bilayered lead iodide hybrid perovskite, (2IPA)2 FAPb2 I7 (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 (>102  mA W-1 ) and significant detectivities (>1012 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.

Low Detection Limit Circularly Polarized Light Detection Realized by Constructing Chiral Perovskite/Si Heterostructures.

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 MAPb2 I7 /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.

Proton-Conductive Polyoxometalate Architectures Constructed from Lanthanide-Incorporated Polyoxoniobate Cages.

Two new extended polyoxometalate (POM) architectures based on lanthanide-incorporated polyoxoniobate (Ln-incorporated PONb) cages, namely, H4[CuII(en)2]4{K4(H2O)2[CuII(en)2]5[CuII5(trz)2(en)4(OH)2][Dy2CuII2(en)2(CO3)3(H2O)2(OH)3][Dy(H2O)4][DyNb23O68(H2O)4]2}·60H2O (1, en = ethylenediamine) and H20[CuII(en)2]4{[CuII(en)2]4[Dy2(C2O4)(H2O)4]2[(Nb32(OH)4(H2O)3O89]2}·54H2O (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.

Two Giant Calixarene-Like Polyoxoniobate Nanocups {Cu12 Nb120 } and {Cd16 Nb128 } Built from Mixed Macrocyclic Cluster Motifs.

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 {Cu12 Nb120 } and {Cd16 Nb128 }. The former integrates three tricyclic Nb24 clusters and a hexacyclic Nb48 cluster into a cup-shaped molecule via a Cu12 metallacalixarene, while the latter unifies two tricyclic Nb24 clusters and a brand-new pentacyclic Nb40 cluster into another cup-shaped molecule via a hybrid Cd16 unit. With 132 and 144 metal centers, {Cu12 Nb120 } and {Cd16 Nb128 } show the largest two inorganic-organic hybrid PONbs known to date.

Proton conductive polyoxoniobate frameworks constructed from nanoscale {Nb68O200} cages.

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 Hybrid Polyoxometalate Framework Based on a Cubic Polyoxoniobate-Cupric-Complex Cage with a High Water Vapor Adsorption Capacity.

A rare 3D porous inorganic-organic polyoxoniobate framework based on the cubic polyoxoniobate-cupric-complex cage {[Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)}} (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 CdSO4-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.

High-dimensional Polyoxoniobates Constructed from Lanthanide-incorporated High-nuclear {[Ln(H2 O)4 ]3 [Nb24 O69 (H2 O)3 ]2 } Secondary Building Units.

In this work, two rare high-dimensional polyoxoniobates with formulas of H9 [Cu(en)(H2 O)2 ][Cu(en)2 ]8 [Dy(H2 O)4 ]3 [Nb24 -O69 (H2 O)3 ]2 ⋅ 36H2 O (1) and H9 K[Cu(en)2 (H2 O)]5 [Cu(en)2 ]4 -[Eu(H2 O)4 ]3 [Nb24 O69 (H2 O)3 ]2 ⋅ 2en ⋅ 45H2 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(H2 O)4 ]3 [Nb24 O69 (H2 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.

Inorganic-Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework.

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 K4 @{[Cu29 (OH)7 (H2 O)2 (en)8 (trz)21 ][Nb24 O67 (OH)2 (H2 O)3 ]4 } and [Cu(en)2 ]@{[Cu2 (en)2 (trz)2 ]6 (Nb68 O188 )} 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 ]@{[Cu2 (trz)2 (en)2 ]6 [H10 Nb68 O188 ]}}. These materials exhibit visible-light-driven photocatalytic H2 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.

Record High-Nuclearity Polyoxoniobates: Discrete Nanoclusters {Nb114 }, {Nb81 }, and {Nb52 }, and Extended Frameworks Based on {Cu3 Nb78 } and {Cu4 Nb78 }.

A series containing the highest nuclearity polyoxoniobate (PONb) nanoclusters, ranging from dimers to tetramers, has been obtained. They include one 114-nuclear {Li8 ⊂Nb114 O316 }, one 81-nuclear {Li3 K⊂Nb81 O225 }, and one 52-nuclear {H4 Nb52 O150 }. The Nb nuclearity of these PONbs is remarkably larger than those of all known high-nuclearity PONbs (≤32). Furthermore, the introduction of 3d Cu2+ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H3 Cu3 Nb78 O222 } or {H3 Cu4 (en)Nb78 O222 }. 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.