Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering.

Oxides have attracted considerable attention owing to their potential for nonlinear optical (NLO) applications. Although significant progress has been achieved in optimizing the structural characteristics of primitives (corresponding to the simplest constituent groups, namely, cations/anions/neutral molecules) comprising the crystalline oxides, the role of the primitives' interaction in determining the resultant functional structure and optical properties has long been underappreciated and remains unclear. In this study, we employ a π-conjugated organic primitive confinement strategy to manipulate the interactions between primitives in antimonates and thereby significantly enhance the optical nonlinearity. Chemical bonds and relatively weak H-bonding interactions promote the formation of cis- and trans-Sb(III)-based dimer configurations in (C5H5NO)(Sb2OF4) (4-HPYSOF) and (C5H7N2)(Sb2F7) (4-APSF), respectively, resulting in very different second-harmonic generation (SHG) efficiencies and birefringences. In particular, 4-HPYSOF displays an exceptionally strong SHG response (12 × KH2PO4 at 1064 nm) and a large birefringence (0.513 at 546 nm) for a Sb(III)-based NLO oxide as well as a UV cutoff edge. Structural analyses and theoretical studies indicate that polarized ionic bond interactions facilitate the favorable arrangement of both the inorganic and organic primitives, thereby significantly enhancing the optical nonlinearity in 4-HPYSOF. Our findings shed new light on the intricate correlations between the interactions of primitives, inorganic primitive configuration, and SHG properties, and, more broadly, our approach provides a new perspective in the development of advanced NLO materials through the interatomic bond engineering of oxides.

Self-assembled stereomutation with supramolecular chirality inversion.

Supramolecular chirality is involved not only in biological events such as gene communication, replication, and enzyme catalysis but also in artificial self-assembly systems and aggregated materials. The precise control of supramolecular chirality, and especially supramolecular chirality inversion (SMCI), would deepen the understanding of chiral transfer and regulation in both living systems and artificial self-assembly systems, providing efficient ways to construct advanced chiral materials with an optimum assembly pathway necessary for various functions. In this review, the fundamental principles of SMCI are comprehensively summarized, with a focus on the helical assemblies having opposite handedness or chiroptical properties of the compositions. Thereafter, various SMCI strategies that have been developed for chiral nanostructures and assembled materials are systematically reviewed, and the promising applications of SMCI, including chiroptical switches, chiral recognition, enantiomeric separation, asymmetric catalysis, chiral optoelectronic materials, chiral spin filters, and biomedical uses, are highlighted accordingly. Finally, the scientific challenges and future perspectives for assembling materials with SMCI are also discussed.

Unlocking Giant Third-Order Optical Nonlinearity in (MA)2CuX4 through Introducing Jahn-Teller Distortion.

Nonlinear absorption coefficient and modulation depth stand as pivotal properties of nonlinear optical (NLO) materials, while the existing NLO materials exhibit limitations such as low nonlinear absorption coefficients and/or small modulation depths, thereby severely impeding their practical application. Here we unveil that introducing Jahn-Teller distortion in a Mott-Hubbard system, (MA)2CuX4 (MA=methylammonium; X=Cl, Br) affords the simultaneous attainment of a giant nonlinear absorption coefficient and substantial modulation depth. The optimized compound, (MA)2CuCl4, demonstrates a nonlinear absorption coefficient of (1.5±0.08)×105 cm GW-1, a modulation depth of 60 %, and a relatively low optical limiting threshold of 1.22×10-5 J cm-2. These outstanding attributes surpass those of most reported NLO materials. Our investigation reveals that a more pronounced distortion of the [CuX6]4- octahedron emerges as a crucial factor in augmenting optical nonlinearity. Mechanism study involving structural and spectral characterization along with theoretical calculations indicates a correlation between the compelling performance and the Mott-Hubbard band structure of the materials, coupled with the Jahn-Teller distortion-induced d-d transition. This study not only introduces a promising category of high-performance NLO materials but also provides novel insights into enhancing the performance of such materials.

Secondary-Bond-Driven Construction of a Polar Material Exhibiting Strong Broad-Spectrum Second-Harmonic Generation and Large Birefringence.

Considerable effort has been invested in the development of non-centrosymmetric (NCS) inorganic solids for ferroelectricity-, piezoelectricity- and, particularly, optical nonlinearity-related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non-directionality and unsaturation of the ionic bonds between metal counter-cations and covalent anionic modules. We report herein a secondary-bond-driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second-harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter-cation-free iodate, VO2 (H2 O)(IO3 ) (VIO), a new class of iodate, crystallizes in a polar lattice with ∞ 1 [ ${{}_{{\rm { \infty }}}{}^{{\rm { 1}}}{\rm { [}}}$ VO2 (H2 O)(IO3 )] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2 PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the ∞ 1 [ ${{}_{{\rm { \infty }}}{}^{{\rm { 1}}}{\rm { [}}}$ VO2 (H2 O)(IO3 )] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high-performance NLO materials.

An Unprecedented [BO2]-Based Deep-Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution.

Solid-state structures with the superhalogen [BO2]- have thus far only been observed with a few compounds whose syntheses require high reaction temperatures and complicated procedures, while their optical properties remain almost completely unexplored. Herein, we report a facile, energy-efficient synthesis of the first [BO2]-based deep-ultraviolet (deep-UV) transparent oxide K9[B4O5(OH)4]3(CO3)(BO2) ⋅ 7H2O (KBCOB). Detailed structural characterization and analysis confirm that KBCOB possesses a rare four-in-one three-dimensional quasi-honeycomb framework, with three π-conjugated anions ([BO2]-, [BO3]3-, and [CO3]2-) and one non-π-conjugated anion ([BO4]5-) in the one crystal. The evolution from the traditional halogenated nonlinear optical (NLO) analogues to KBCOB by superhalogen [BO2]- substitution confers deep-UV transparency (<190 nm), a large second-harmonic generation response (1.0×KH2PO4 @ 1064 nm), and a 15-fold increase in birefringence. This study affords a new route to the facile synthesis of functional [BO2]-based oxides, paving the way for the development of next-generation high-performing deep-UV NLO materials.

Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates.

The development of deep-ultraviolet (DUV)/solar-blind UV nonlinear optical (NLO) crystals simultaneously possessing wide UV transparency, strong second-harmonic generation (SHG) response, and suitable birefringence is a major challenge in advanced laser technology. We herein propose a "cation compensation" strategy for strong optical nonlinearity in inorganic solids that is exemplified by the introduction of strongly electropositive transition metals (TMs). Following this strategy, the first d0 TM UV-transparent NLO sulfates, MF2(SO4) (M = Zr (ZFSO), Hf (HFSO)), have been synthesized. Short UV cutoff edges of 206 nm and below 190 nm are observed for bulk ZFSO and HFSO crystals, respectively, together with the strongest powder SHG responses (3.2 × (ZFSO) and 2.5 × KDP (HFSO)) for solar-blind UV/DUV NLO sulfates, as well as suitable birefringence. This work provides a new and efficient approach to the development of urgently needed high-performance NLO materials for applications in the short-wavelength UV region.

Giant Mid-Infrared Second-Harmonic Generation Response in a Densely-Stacked Van Der Waals Transition-Metal Oxychloride.

Second-harmonic generation (SHG) is a fundamental optical property of nonlinear optical (NLO) crystals. Thus far, it has proved difficult to engineer large SHG responses, particularly in the mid-infrared region, owing to the difficulty in simultaneously controlling the arrangement and density of functional NLO-active units. Herein, a new assembly strategy employing functional modules only, and aimed at maximizing the density and optimizing the spatial arrangement of highly efficient functional modules, has been applied to the preparation of NLO crystals, affording the van der Waals crystal MoO2 Cl2 . This exhibits the strongest powder SHG response (2.1×KTiOPO4 (KTP) @ 2100 nm) for a transition-metal oxyhalide, a wide optical transparency window, and a sufficient birefringence. MoO2 Cl2 is the first SHG-active transition-metal oxyhalide effective in the infrared region. Theoretical studies and crystal structure analysis suggest that the densely packed, optimally-aligned [MoO4 Cl2 ] modules within the two-dimensional van der Waals layers are responsible for the giant SHG response.

Quadruple-Bidentate Nitrate-Ligated A2 Hg(NO3 )4 (A=K, Rb): Strong Second-Harmonic Generation and Sufficient Birefringence.

The design of efficient nonlinear optical (NLO) crystals continues to pose significant challenges due to the difficulty of assembling polar NLO-active modules in an optimal additive fashion. We report herein the first NLO-active mercuric nitrates A2 Hg(NO3 )4 (A=(KHNO), Rb (RHNO)), for which assembly is induced by ionic polarization of the d10 cations. The two new crystalline compounds are isostructural, featuring interesting pseudo-diamond-like structures with parallel [Hg(NO3 )4 ] modules, and leading to strong powder second-harmonic generation (SHG) responses of 9.2 (KHNO) and 8.8 (RHNO) times that of KH2 PO4 . In combination with the simple solution preparation of centimeter-scale crystals, sufficient birefringence, and short ultraviolet (UV) cutoff edges, these attributes make KHNO and RHNO promising candidates for UV NLO materials. Theoretical calculations and single-crystal structure analysis reveal that the newly-developed highly condensed and distorted [Hg(NO3 )4 ] module, with an Hg2+ cation that is quadruply bidentate nitrate-ligated, is crucial for the significant SHG responses. This work highlights the potential importance of modules with multiple bidentate ligands for the development of high-performing next-generation NLO materials.

Ultrashort Phase-Matching Wavelength and Strong Second-Harmonic Generation in Deep-UV-Transparent Oxyfluorides by Covalency Reduction.

The development of urgently-needed ultraviolet (UV)/deep-UV nonlinear optical (NLO) materials has been hindered by contradictory requirements of the microstructure, in particular the need for a strong second-harmonic generation (SHG) response as well as a short phase-matching (PM) wavelength. We herein employ a "de-covalency" band gap engineering strategy to adjust the optical linearity and nonlinearity. This has been achieved by assembling two types of transition-metal (TM) polyhedra ([TaO2 F4 ] and [TaF7 ]), affording the first tantalum-based deep-UV-transparent NLO materials, A5 Ta3 OF18 (A = K (KTOF), Rb (RTOF)). Experimental and theoretical studies reveal that the highly ionic bonds and strong electropositivity of tantalum in the two oxyfluorides induce record short PM wavelengths (238 (KTOF) and 240 (RTOF) nm) for d0 -TM-centered oxides, in addition to strong SHG responses (2.8 × KH2 PO4 (KTOF) and 2.6 × KH2 PO4 (RTOF)), and sufficient birefringences (0.092 (KTOF) and 0.085 (RTOF) at 546 nm). These results not only broaden the available strategies for achieving deep-UV NLO materials by exploiting the currently neglected d0 -TMs, but also push the shortest PM wavelength into the short-wavelength UV region.

Isoreticular Design of KTiOPO4-Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation.

Second-harmonic generation (SHG) is of great technological importance for applications in nonlinear optics, but it remains challenging to engineer large SHG responses in the short-wavelength ultraviolet (UV) region owing to competing microstructure requirements. Herein, we report the first examples of d0 transition-metal-based (TM-based) deep-UV-transparent nonlinear optical (NLO) crystals MOF4H2 (M = Zr (ZOF), Hf (HOF)), which exhibit unprecedented short UV absorption edges (below 190 nm). Evolving from the KTiOPO4 (KTP) structure by an isoreticular node substitution strategy, the three-dimensional frameworks of ZOF and HOF consist of corner-sharing [MO2F6] moieties that are new functional units in deep-UV NLO material design, conferring wide UV transparency and strong phase-matchable SHG response (2.2 × KH2PO4 (ZOF) and 1.8 × KH2PO4 (HOF) at 1064 nm). Such d0-TM-based [MO2F6] polyhedra preclude deleterious d-d electronic transitions, resulting in significantly blue-shifted UV absorption edges of ZOF and HOF (<190 nm). The d0-TM-based [MO2F6] polyhedra introduced in this work offer a new perspective in the construction of deep-UV transparent NLO materials, demonstrating the feasibility of an isoreticular design strategy in developing functional NLO materials.

Outstanding Multi-Photon Absorption at π-Delocalizable Metallodendrimers.

Multi-photon absorption (MPA) has attracted interest for applications exploiting the tight spatial control of interaction volume and long wavelength excitation. However, a deficiency of molecules exhibiting higher-order nPA (n-photon absorption, n>2) and a lack of structure-property studies to define the key structural characteristics needed to optimize higher-order MPA performance have hindered practical development. We herein report the syntheses of second- and third-generation metallodendrimers and assessment of their nonlinear absorption, together with those of zero- and first-generation analogues. We report the first 5PA and 6PA data for an organometallic. The largest dendrimer exhibits exceptional three-, four-, five- and six-photon absorption to femtosecond-pulsed light. The systematically varied compounds highlight the crucial role of metal-to-oligo(phenyleneethynylene) charge transfer in promoting outstanding MPA activity.

Giant Multi-Photon Absorption by Heptazine Organometalation.

Multi-photon absorption (MPA) is of increasing interest for applications in technologically important "windows" of the electromagnetic spectrum (near-infrared III, NIR-III, 1550-1870 nm; and the new 2080-2340 nm region); however, few molecules exist that display strong MPA at these long wavelengths. We herein report the syntheses of the first 2,5,8-s-heptazine-cored organometallic complexes, together with organic analogues. The complexes exhibit outstanding 3PA cross-sections in the NIR-III and exceptional 4PA cross-sections in the new 2080-2340 nm window. We demonstrate that replacing organic donor groups by organometallic units results in an order of magnitude increase in 3PA, the "switching on" of 4PA, and a dramatic improvement in photo-stability. Our results highlight the impressive outcomes possible with an "organometalation" approach to NLO materials design.

Ultrawide Bandgap and Outstanding Second-Harmonic Generation Response by a Fluorine-Enrichment Strategy at a Transition-Metal Oxyfluoride Nonlinear Optical Material.

The development of nonlinear optical (NLO) materials has been hindered by competing microstructure requirements: the need to simultaneously engineer a large hyperpolarizability (a large second-harmonic generation (SHG)) and a wide HOMO-LUMO gap (a wide band gap). Herein, a non-centrosymmetric transition-metal (TM) oxyfluoride K5 (NbOF4 )(NbF7 )2 (KNOF) with an extremely high F/O ratio is constructed in high yield. KNOF exhibits an extremely wide band gap (5.88 eV) and a strong powder SHG response (4.0×KH2 PO4 )-both being the largest values for TM-centered oxyfluorides-as well as a birefringence sufficient for applications. The dominant roles of the partially fluorinated [NbO2 F4 ] and totally fluorinated [NbF7 ] groups in achieving the enlarged band gap in KNOF have been clarified by first-principles calculations. Our results suggest that maximizing the fluorine content of oxyfluorides may unlock the promise of short-wavelength-transparent materials with exceptional NLO performance.

Additive-Triggered Polar Polymorph Formation: ß-Sc(IO3 )3 , a Promising Next-Generation Mid-Infrared Nonlinear Optical Material.

Noncentrosymmetric (NCS) solids have attracted interest for their potential in ferroelectric, piezoelectric, and nonlinear optical (NLO) devices, but their synthesis remains a major challenge. In this study, the additive Li2 CO3 triggers formation of an NCS precursor at an early nucleation stage, and plays a crucial role in the successful polymorphism transformation. The resultant metastable ß-Sc(IO3 )3 is a promising mid-infrared NLO crystal, with the strongest second-harmonic generation responses (2.2×KTiOPO4 @ 2100 nm, 16×KH2 PO4 @ 1064 nm) and the largest optical band gap (4.52 eV) for a rare-earth iodate, as well as sufficient birefringence (Δn=0.219 @ 546 nm) for type I phase-matching, and wide optical transparency, which are induced by optimal alignment of the iodate anions. This study reveals the key role of additives in the growth of polar NCS solids, a discovery with implications for the strategic design of new NCS polymorphism materials with exceptional NLO properties.

A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep-UV Transparency.

The targeted synthesis of deep-ultraviolet (deep-UV) nonlinear optical (NLO) materials, especially those with non-π-conjugated sulfates, has experienced considerable difficulties due to the need to reconcile the oft-competing requirements for deep-UV transparency and strong second-harmonic generation (SHG). We report herein the designed synthesis of the first rare-earth metal-based deep-UV sulfate La(NH4 )(SO4 )2 by a double-salt strategy involving introduction of complementary cations, together with optical studies that reveal a short-wavelength deep-UV absorption edge (below 190 nm) and the strongest SHG response among deep-UV NLO sulfates (2.4×KDP). Theoretical calculations and crystal structure analysis suggest that the excellent balance between SHG response and deep-UV transparency can be attributed to a synergistic interaction of the hetero-cations La3+ and [NH4 ]+ , which optimize alignment of the [SO4 ] tetrahedra and highly polarizable [LaO8 ] polyhedra.

Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra.

Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.

Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo2O8F.

Strong second-harmonic generation (SHG) and a wide band gap are two crucial but often conflicting parameters that must be optimized for practical nonlinear optical (NLO) materials. We report herein the first d0-transition-metal (TM) tellurite with half of the d0-TM-octahedra partially fluorinated, namely, quinary RbTeMo2O8F, which exhibits giant SHG responses (27 times that of KH2PO4 (KDP) and 2.2 times that of KTiOPO4 (KTP) with 1064 and 2100 nm laser radiation, respectively), the largest SHG values among all reported metal tellurites. RbTeMo2O8F also possesses a large band gap (3.63 eV), a wide optical transparency window (0.34-5.40 µm), and a significant birefringence (Δn = 0.263 at 546 nm). Theoretical calculations and crystal structure analysis demonstrate that the outstanding SHG responses can be definitively attributed to the uniform alignment of the polarized [MoO5F]/[MoO6] octahedra and the seesaw-like [TeO4], and the consequent favorable summative polarization of the three distinct SHG-active polyhedra, both induced by partial fluorine substitution on the [MoO6] octahedra.

Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution.

Materials capable of generating coherent short-wave (<300 nm) light have attracted extensive scientific and technical interest due to their wide utilization in laser research. In this study, a the rare-earth-metal sulfate NaCe(SO4)2(H2O) (NCSO) was synthesized through a hydrothermal method, while NaBi(SO4)2(H2O) (NBSO) was successfully obtained via a homovalent cation substitution of the parent compound NCSO under hydrothermal conditions. The space groups of crystalline NCSO and NBSO are P3121 and P3221, respectively. Both compounds have similar connectivities which feature a three-dimensional channel structure formed by asymmetric [CeO9]15-/[BiO9]15- tricapped trigonal prisms and distorted [SO4]2- tetrahedra. The introduction of Bi3+ with larger ionic radii and stereochemically active lone-pair electrons simultaneously enhanced the SHG effect and band gap of NBSO in comparison to its parent compound NCSO. In contrast to NCSO, which possesses a narrow energy band gap (2.46 eV), NBSO displays the largest energy band gap (4.54 eV) among the reported bismuth sulfate NLO materials. Powder frequency-doubling-effect measurements exhibit that NCSO and NBSO possess phase-matchable SHG responses of 0.2 × KDP and 0.38 × KDP at 1064 nm, respectively. Theoretical studies have been implemented to further elucidate the structure-performance relationships of the two compounds. Experimental and theoretical studies both demonstrate that NBSO may be a promising nonlinear material applied in the short-wavelength region.

Two-photon absorption properties of multipolar triarylamino/tosylamido 1,1,4,4-tetracyanobutadienes.

The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives (1, 3c and 4b-c) incorporating tosylamido and 4-triphenylamino moieties are reported. Along with those of five closely related or differently branched TCBDs derivatives (2, 3a-b, 4c and 5), their linear and (third-order) nonlinear optical properties were investigated by electronic absorption spectroscopy and Z-scan measurements. Among these compounds, the tri-branched compounds 3c and 5 are the most active two-photon absorbers, with effective cross-sections of 275 and 350 GM at 900 nm, respectively. These properties are briefly discussed with the help of DFT calculations, focussing on structural and electronic factors, and contextualized with results obtained previously for related compounds.

Transition metal complex/gold nanoparticle hybrid materials.

Gold nanoparticles (AuNPs) are of considerable interest for diverse applications in areas such as medicine, catalysis, and sensing. AuNPs are generally surface-stabilized by organic matrices and coatings, and while the resultant organic compound (OC)/AuNP hybrids have been explored extensively, they are not suitable for certain applications (e.g. those necessitating reversible redox behaviour and/or long excited-state lifetimes), and they often suffer from low photo- and/or thermal stability. Transition metal complex (TMC)/AuNP hybrids have recently come to the fore as they circumvent some of the aforementioned shortcomings with OC/AuNP hybrids. This review summarizes progress thus far in the nascent field of TMC/AuNP hybrids. The structure and composition of extant TMC/AuNP hybrids are briefly reviewed and the range of TMCs employed in the shell of the hybrids are summarized, the one-phase, two-phase, and post-nanoparticle-synthesis synthetic methods to TMC/AuNP hybrids are discussed and contrasted, highlighting the advantages of variants of the last-mentioned procedure, and the utility of the various characterization techniques is discussed, emphasizing the need to employ multiple techniques in concert. Applications of TMC/AuNP hybrids in luminescence, electrochemical, and electro-optical sensing are described and critiqued, and their uses and potential in imaging, photo-dynamic therapy, nonlinear optics, and catalysis are assessed.