Refining the phylogeny and taxonomy of the apple tribe Maleae (Rosaceae): insights from phylogenomic analyses of 563 plastomes and a taxonomic synopsis of Photinia and its allies in the Old World.

This study addresses the longstanding absence of a comprehensive phylogenetic backbone for the apple tribe Maleae, a deficiency attributed to limited taxon and marker sampling. We conducted an extensive taxon sampling, incorporating 563 plastomes from a diverse range of 370 species encompassing 26 presently recognized genera. Employing a range of phylogenetic inference methods, including RAxML and IQ-TREE2 for Maximum Likelihood (ML) analyses, we established a robust phylogenetic framework for the Maleae tribe. Our phylogenomic investigations provided compelling support for three major clades within Maleae. By integrating nuclear phylogenetic data with morphological and chromosomal evidence, we propose an updated infra-tribal taxonomic system, comprising subtribe Malinae Reveal, subtribe Lindleyinae Reveal, and subtribe Vauqueliniinae B.B.Liu (subtr. nov.). Plastid phylogenetic analysis also confirmed the monophyly of most genera, except for Amelanchier, Malus, Sorbus sensu lato, and Stranvaesia. In addition, we present a comprehensive taxonomic synopsis of Photinia and its morphological allies in the Old World, recognizing 27 species and ten varieties within Photinia, three species and two varieties within Stranvaesia, and two species and three varieties within Weniomeles. Furthermore, we also lectotypified 12 names and made two new combinations, Photiniamicrophylla (J.E.Vidal) B.B.Liu and Weniomelesatropurpurea (P.L.Chiu ex Z.H.Chen & X.F.Jin) B.B.Liu.

Nightmare or delight: Taxonomic circumscription meets reticulate evolution in the phylogenomic era.

Phylogenetic studies in the phylogenomics era have demonstrated that reticulate evolution greatly impedes the accuracy of phylogenetic inference, and consequently can obscure taxonomic treatments. However, the systematics community lacks a broadly applicable strategy for taxonomic delimitation in groups characterized by pervasive reticulate evolution. The red-fruit genus, Stranvaesia, provides an ideal model to examine the influence of reticulation on generic circumscription, particularly where hybridization and allopolyploidy dominate the evolutionary history. In this study, we conducted phylogenomic analyses integrating data from hundreds of single-copy nuclear (SCN) genes and plastomes, and interrogated nuclear paralogs to clarify the inter/intra-generic relationship of Stranvaesia and its allies in the framework of Maleae. Analyses of phylogenomic discord and phylogenetic networks showed that allopolyploidization and introgression promoted the origin and diversification of the Stranvaesia clade, a conclusion further bolstered by cytonuclear and gene tree discordance. With a well-inferred phylogenetic backbone, we propose an updated generic delimitation of Stranvaesia and introduce a new genus, Weniomeles. This new genus is distinguished by its purple-black fruits, thorns trunk and/or branches, and a distinctive fruit core anatomy characterized by multilocular separated by a layer of sclereids and a cluster of sclereids at the top of the locules. Through this study, we highlight a broadly-applicable workflow that underscores the significance of reticulate evolution analyses in shaping taxonomic revisions from phylogenomic data.

Malus includes Docynia (Maleae, Rosaceae): evidence from phylogenomics and morphology.

Docynia has been treated as a separate genus or merged into Cydonia or Docyniopsis. Our phylogenomic evidence from 797 single-copy nuclear genes and plastomes confirmed the sister relationship between Docynia and Docyniopsis. By integrating the phylogenomic and morphological evidence, we propose to accept a broad generic concept of Malus and merge Docynia into Malus. Three new combinations are also made here: Malusdelavayi (Franch.) B.B.Liu, M.indica (Wall.) B.B.Liu and M.longiunguis (Q.Luo & J.L.Liu) B.B.Liu.

Water-Stable Hybrid Lead-Free Perovskite for Negative Temperature Coefficient Thermistors.

Negative temperature coefficient (NTC) thermistors feature higher sensitivities and faster response speeds and thereby have particular applications in many fields. However, current NTC thermistors are mostly based on inorganic ceramic materials, which show obvious drawbacks in material synthesis, property modulation, and flexible film fabrication. Herein, we report, for the first time, the promising application of an inorganic-organic hybrid NTC thermistor. A new lead-free hybrid iodo bismuthate [1,1',1″-(benzene-1,3,5-triyl)tris(3-methyl-1H-imidazol-3-ium)]Bi2I9 [denoted as (Me3TMP)Bi2I9] was synthesized by a "double-free" strategy. (Me3TMP)Bi2I9 features a lead-free binuclear bismuth iodine anion charge compensated by a "classic hydrogen-bond-free" cation. (Me3TMP)Bi2I9 exhibits remarkable stability in water and UV light irradiation and shows the largest temperature sensitivity coefficient among all reported NTC materials. Theoretical calculation and detailed structural analysis disclose that the seriously distorted (BiI6) octahedra are responsible for the intriguing NTC effect for (Me3TMP)Bi2I9.

Ultrathin covalent and cuprophilic interaction-assembled copper-sulfur monolayer in organic metal chalcogenide for oriented photoconductivity.

We report the thinnest copper sulfur atomic monolayer in an organic copper chalcogenide [Cu(CMP)]n (CMP = 5-chloro-2-mercaptopyridine). The layer features a new type of copper sulfur structure woven by both covalent bond and cuprophilic interaction and shows an intriguing oriented photoconductivity.

The complete chloroplast genome sequence of Magnolia mexicana DC. (Magnoliaceae) from Central America.

The chloroplast genome of the Magnolia species from Central America has never been reported. With its local use for food flavoring, medicine, and wood, M. mexicana has been of good economic importance. In the present study, the complete chloroplast genome of M. mexicana was assembled via the genome skimming data. As a typical quadripartite structure, the plastome of M. mexicana with 159,906 bp in length includes two inverted repeats (26,554 bp) separated by a small single copy region (18,761 bp) as well as a large single copy region (88,037 bp). This chloroplast genome consists of 131 different genes, including 86 protein coding genes (CDS), eight rRNA genes, and 37 tRNA genes. The maximum likelihood phylogenetic analysis showed that M. mexicana from Central America was closely related to an evergreen species, M. odoratissima from East Asia.

Design, Synthesis, and Photocatalytic Application of Moisture-Stable Hybrid Lead-Free Perovskite.

The employment of hybrid perovskite MAPbX3 (MA = CH3NH3+, X = Br or I) as photocatalysts in a photocatalytic hydrogen evolution reaction represents a promising approach to store solar energy. However, the toxicity of Pb makes these materials difficult to pass environmental evaluation while the intrinsic moisture sensitivity puts forward high anhydrous requirements in photocatalysts synthesis, storage, and application, which further reduces their service life. Herein, we demonstrate a hydrogen-bond-free strategy to synthesize moisture-stable hypotoxic hybrid perovskite for photocatalytic application by replacing traditional protonated countercations with alkylated countercations in a Pb-free hybrid system, which prevents water eroding hybrid perovskites via strong hydrogen bonds. A zero-dimensional Bi-based perovskite (3-ethylbenzo[d]thiazol-3-ium)4Bi2I10 (EtbtBi2I10) was synthesized, which contains dimeric (Bi2I10)4- formed by edge-sharing (BiI6) octahedra being different from the binuclear cluster in widely studied MA3Bi2I9. Theoretical calculations indicate that the electron communication between inorganic and organic moieties is responsible for its broadband absorption with a narrow band gap of 2.04 eV. EtbtBi2I10 exhibits excellent stability in distilled water, moisture air, acid solution, and UV-light irradiation. It shows effective photocatalytic performance in HI splitting to generate hydrogen with the performance comparable with MAPbI3. Introducing electron and hole-transporting channels drastically enhances the photocatalytic reaction.

Typification of 23 names in Eriobotrya (Maleae, Rosaceae).

As part of a comprehensive systematic study on the genus Eriobotrya and its close relatives from the E & SE Asia, new typifications of 23 names are presented here, along with some nomenclatural notes of the names involved. We lectotypified 22 names including accepted names and synonyms. They are: E. acuminatissima, E. bengalensis var. angustifolia; E. bengalensis f. intermedia, E. brackloi, E. brackloi var. atrichophylla, E. elliptica var. petelotii, E. fragrans var. furfuracea, E. glabrescens, E. grandiflora, E. henryi, E. oblongifolia, E. petiolata, E. platyphylla, E. poilanei, E. prinoides, E. prinoides var. laotica, E. salwinensis, E. serrata, E. stipularis, Hiptage cavaleriei, Photinia longifolia, Symplocos seguinii. One neotype of Photinia dubia was also proposed in this study, and E. pseudoraphiolepis and Mespilus cuila were identified as superfluous names. In addition, we also summarized the typification of 18 names for taxonomic reference: E. angustissima, E. balgooyi, E. condaoensis, E. × daduheensis, E. elliptica, E. fulvicoma, E. fragrans, E. glabrescens var. victoriensis, E. hookeriana, E. latifolia, E. obovata, E. malipoensis, E. merguiensis, E. tengyuehensis, E. wardii, Mespilus bengalensis, Photinia deflexa, and M. japonica.

Poly(sodium 4-styrenesulfonate) Assisted Room-Temperature Synthesis for the Mass Production of Bismuth Oxychloride Ultrathin Nanoplates with Enhanced Photocatalytic Activity.

Bismuth oxychloride ultrathin nanoplates (BiOCl-UTNs) are highly active, but their preparation are limited to closed-vessel hydrothermal and solvothermal techniques at high temperatures (110-180 °C). Here we report a straightforward poly(sodium 4-styrenesulfonate) (PSS)-mediated route for the large-scale synthesis of BiOCl-UTNs at room-temperature. In an open vessel, 6.15 g of BiOCl-UTNs with 3-5 nm thickness, and planar dimensions of 30-50 nm were produced. The strong electrostatic interaction between PSS and [Bi2 O2 ]2+ layers inhibited the growth rate of BiOCl nanoplates along <001> direction, and Na+ ions governed the electrolyte sedimentation to produce BiOCl-UTNs. The resulting BiOCl-UTNs exhibited high photocatalytic activity for the degradation of antibiotics and organic dyes because of their large specific surface area, increased light absorption ability, and fast separation and transfer efficiency of the photoexcited charge carriers.

Eriobotrya Belongs to Rhaphiolepis (Maleae, Rosaceae): Evidence From Chloroplast Genome and Nuclear Ribosomal DNA Data.

The Eriobotrya-Rhaphiolepis (ER) clade consists of about 46 species distributed in East and Southeast Asia. Although Eriobotrya and Rhaphiolepis have been supported to form a clade, the monophyly of Eriobotrya and Rhaphiolepis at the genus level has never been well tested and their phylogenetic positions in Maleae still remain uncertain. This study aims to reconstruct a robust phylogeny of the ER clade in the framework of Maleae with a broad taxon sampling and clarify the phylogenetic relationship between Eriobotrya and Rhaphiolepis. This study employed sequences of the whole plastome (WP) and entire nuclear ribosomal DNA (nrDNA) repeats assembled from the genome skimming approach and included 83 samples representing 76 species in 32 genera of Rosaceae, especially Maleae. The Maximum Likelihood (ML) and Bayesian Analysis (BI) based on three datasets, i.e., WP, coding sequences of plastome (CDS), and nrDNA, strongly supported the paraphyly of Eriobotrya, within which Rhaphiolepis was nested. Our plastid tree supported the sister relationship between the ER clade and Heteromeles, and the nrDNA tree, however, did not resolve the phylogenetic placement of the ER clade in Maleae. Strong incongruence between the plastid and the nuclear trees is most likely explained by hybridization events, which may have played an important role in the evolutionary history of the ER clade. Molecular, morphological, and geographic evidence all supports the merge of Eriobotrya with Rhaphiolepis, which has the nomenclatural priority. We herein transferred 36 taxa of Eriobotrya to Rhaphiolepis. We also proposed a new name, Rhaphiolepis loquata B.B.Liu & J.Wen, for the economically important loquat, as the specific epithet "japonica" was pre-occupied in Rhaphiolepis.

The structures, water stabilities and photoluminescence properties of two types of iodocuprate(i)-based hybrids.

Although great progress has been made in hybrid iodocuprates(i) as lighting phosphors, the effects of aromatic and aliphatic structure directing agents (SDAs) on their water stability, structure and photoluminescence (PL) properties are still not clear. Herein, aromatic N-heterocyclic 1,2-di(4-pyridyl)ethylene (dpe), aliphatic N-heterocyclic 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) and N-aminoethylpiperazine (app) were selected to be SDAs to construct two types of hybrid iodocuprates(i) via a facile in situ approach. Aromatic dpe-derived cations are successfully directed to form (Me2dpe)(CuI3) (1), (Me2dpe)n(Cu4I6)n (2), (Et2dpe)2(Cu6I10) (3), and (H2dpe)n(Cu2I4)n (4). Three of them contain unprecedented inorganic iodocuprate clusters or chains. The aliphatic N-heterocyclic dbu- and app-derivative cations are responsible for the formation of (Hdbu)n(Cu2I3)n (5) and (H3app)2(Cu2I6)·2I·2H2O (6), which contain a (Cu2I3)- chain and a (Cu2I6)4- binuclear cluster, respectively. For the first time, the influence mechanisms of the water stabilities of iodocuprate-based PL materials were disclosed, by analyzing the possible interactions between SDAs and water molecules. 1-2 are PL silent due to their "self-quenching effect". 3, 4 and5 exhibit bright red, orange and yellow solid-state PL emissions at room temperature respectively, originating from the charge transfer between inorganic iodocuprate species and organic N-heterocycles. The co-template approach leads to multiple charge transfers in 6, which features a tunable PL behavior from bluish green to white by varying the excitation light, and has a quantum yield up to 43% (the highest value among hybrid iodocuprates containing (Cu2I6)4- clusters). The comparative study not only helps us to rationally synthesize iodocuprate-based PL materials with enhanced performance, but also provides a new method to obtain wavelength-dependent PL materials.

Do alkyl groups on aromatic or aliphatic structure directing agents affect water stabilities and properties of hybrid iodoargentates?

Two types of in situ formed structure directing agents (SDAs) including aromatic triphenylphosphine (PPh3)- and aliphatic piperazine (H2pp)-derivative cations were used to synthesize five new hybrid iodoargentates, namely (EtPPh3)Ag3I4 (1, Et = ethyl), (n-PrPPh3)Ag3I4 (2, n-Pr = n-propyl), (i-PrPPh3)Ag5I6 (3, i-Pr = isopropyl), (Me4pp)0.5AgI2 (4, Me = methyl), and (H3app)2(Ag2I6)·2I·2H2O (5, app = N-aminoethylpiperazine). A comparative study of the two types of SDAs on the structures, stabilities and properties of hybrid iodoargentates was performed in detail. Structurally, except for (EtPPh3)+ and (n-PrPPh3)+, which both directly form (Ag3I4)- anionic chains in 1 and 2, three SDAs generate hybrid iodoargentates different from each other with inorganic anions ranging from a 0-D (Ag2I6)4- dimer to 1-D α-type (AgI2)- and (Ag5I6)- chains. With regard to the electronic structures, aromatic PPh3-derivative cations make noticeable contributions to the bottom of the conduction bands, while aliphatic pp-derivative cations make nearly no contribution to the frontier orbitals, clearly indicating their different ways to adjust the band gaps. With regard to stability, the decomposition temperatures of 1-3 in the range of 324-349 °C are noticeably higher than the values of 217 and 225 °C for 4 and 5. Furthermore, 1-4 exhibit good water stabilities, which is ascribed to the alkylation reactions precluding the formation of strong hydrogen bonds between alkylated SDAs and extraneous H2O molecules. Contrarily, the presence of typical hydrophilic [double bond, length as m-dash]NH2+, [triple bond, length as m-dash]NH+ and -NH3+ groups on the protonated (H3app)3+ cation makes 5 sensitive to water and a hydrolysis reaction occurs to generate a cubic AgI phase. Finally, 1-3 exhibit high photocatalytic efficiencies for the degradation of rhodamine B (RhB) dye in wastewater under visible light. All conclusions obtained here will help a lot in the synthesis of stable functional metal halide-based hybrids.

Water Stability Studies of Hybrid Iodoargentates Containing N-Alkylated or N-Protonated Structure Directing Agents: Exploring Noncentrosymmetric Hybrid Structures.

In situ alkylation or protonation reactions on the thiazolyl-N donors of benzothiazole (btz) and its derivative 2-aminobenzothiazole (abtz) occurred to form four structure directing agents (SDAs), which feature different structure directing abilities and hydrophobicities. The thiazolyl-N alkylated and protonated btz cations direct to form an α-type (AgI2)- iodoargentate chain in (Etbtz)(AgI2) (1), (Prbtz)(AgI2) (2), and (Hbtz)(AgI2) (3), respectively, while the thiazolyl-N protonated abtz cation directs to form a new type of (Ag2I3)- anionic chain in (Habtz)(Ag2I3) (4). Compounds 1 and 4 represent the first noncentrosymmetric (NCS) hybrid iodoargentates with organic S-containing N-heterocycle derivative cations as SDAs. Further, 1 exhibits high water stability and is second harmonic generation (SHG) active with a response about twice that of KDP (KH2PO4). Importantly, the water stability studies indicate that hybrid iodoargentates with hydrophobic N-alkylated SDAs are more stable in water than those with relative hydrophilic N-protonated SDAs.

A simultaneous disulfide bond cleavage, N,S-bialkylation/N-protonation and self-assembly reaction: syntheses, structures and properties of two hybrid iodoargentates with thiazolyl-based heterocycles.

Solvothermal reactions of AgI with the vulcanization accelerator 2,2'-dibenzothiazolyl disulfide and hydroiodic acid in alcohols afford two hybrid iodoargentates with one-dimensional structures, namely (Et2mbt)[Ag2I3] (1, Hmbt = 2-mercaptobenzothiazole) and {(Hmbt)[AgI]}n (2). The syntheses of both 1 and 2 involve unprecedented multiple in situ reactions. Specifically, a simultaneous disulfide bond cleavage, N and S donor atoms bialkylation, and self-assembly reaction lead to 1 that contains a discrete N,S-biethylated cation (Et2mbt)+ and a rare inorganic (Ag2I3)- anionic chain, while a simultaneous disulfide bond cleavage, N-protonation and self-assembly reaction affords 2 which features zwitterionic Hmbt molecules coordinating with the opposite side Ag atoms of a neutral inorganic (AgI)n chain via forming Ag-S coordination bonds. The simultaneous alkylation on a thiazolyl-N donor and a thiol-S donor atom for a thiazolyl-based heterocycle using inexpensive alcohols and haloids under solvothermal conditions instead of traditional two-step organic synthesis was found for the first time. The two compounds have band gaps of 2.95 eV for 1, and 2.78 eV for 2 exhibiting an observed blue shift compared with bulk AgI. Also, 1 and 2 can be used as effective heterogeneous photocatalysts for methyl orange dye treatment under UV light irradiation.

Structures and multiple properties of two polar metal-organic frameworks based on achiral N,O-coordinated ligands: toward multifunctional materials.

Two novel metal-organic frameworks (MOFs) [Cd3(padc)(Hpadc)(H2padc)(H2O)]n·nH2O (1, H3padc = pyrazole-3,5-dicarboxylic acid) and [Co4(pidc)2(Hpidc)4(H2O)3]n·12nH2O (2, H2pidc = pyridine-2,5-dicarboxylic acid), that both crystallize in polar space groups, were solvothermally synthesized by using achiral N,O-coordinated ligands. Compound 1 consists of trinuclear Cd(II)-based units that are further bridged by the backbone of H3padc ligands to form a three-dimensional (3-D) (4,6)-connected fsc topology network, while compound 2 features two types of double-helical tubes with different chiralities connecting with each other alternatively to construct a typical 2-D (3,6)-connected kgd topology network. Importantly, 1 exhibits combined properties of photoluminescence (PL) and second harmonic generation (SHG), and represents the first noncentrosymmetric H3padc-based MOF that was obtained without any ancillary ligands. While 2 shows strong antiferromagnetic interactions between paramagnetic Co(II) centers, and the aqueous solution of 2 exhibits effective homogeneous photocatalysis properties under visible irradiation. Further, the mechanisms of the physical properties of 1 and 2 are discussed in detail.

A comparison study of aliphatic and aromatic structure directing agents influencing the crystal and electronic structures, and properties of iodoplumbate hybrids: water induced structure conversion and visible light photocatalytic properties.

The introduction of the aliphatic amines en (ethylenediamine), aep (N-(2-aminoethyl)piperazine) and tepa (tetraethylenepentamine), and the aromatic species 2,2'-bipy (2,2'-bipyridine) and dpe (1,2-di(4-pyridyl)ethylene) as structure directing agents (SDAs) into inorganic iodoplumbates affords six hybrids, namely [(Hen)4(H2.5O)2I](PbI6) (1), Cs2n[Pb3I8(en)2]n (2), (H3tepa)n(PbI5)n (3), (H2aep)n(PbI4)n (4), (Et22,2'-bipy)n(Pb2I6)n (5) and (Et2dpe)n(Pb2I6)n (6). 1 contains a discrete octahedral (PbI6)(4-) anion generated under the direction of a novel co-template, [(Hen)4(H2.5O)2I](4+). 2 contains inorganic Cs(+) ions and a novel hybrid anionic layer [Pb3I8(en)2]n(2n-) that has never been encountered in iodoplumbate hybrids. 3 features a zigzag (PbI5)(3-) chain with the charge being compensated by a triprotonated tepa cation. 4 is composed of perovskite sheets of lead(ii) octahedra and aep cations that are generated from tepa via an unprecedented in situ ligand reaction. Both 5 and 6 have (Pb2I6)n(2n-) chains and represent the first example of introducing a 2,2'-bipy or dpe derivative cation in iodoplumbate hybrids, respectively. The comparative study reveals that aliphatic amines and aromatic species contribute differently to the crystal and electronic structures, and the properties of the hybrids. Importantly, 1-4 exhibit interesting water induced structure conversions, while 5 and 6 can be used as heterogeneous photocatalysts for dye wastewater treatment under visible light irradiation.

Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine.

Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

Novel single-crystal's voltage-dependent effect and magnetic order of Ln2ZrQ5 (Ln = La, Sm, Gd; Q = S, Se) semiconductors.

A series of rare-earth zirconium chalcogenides Ln(2)ZrQ(5) (Ln = La, Sm, Gd; Q = S, Se) synthesized by using boron as the reducing reagent show unprecedented single-crystal's intrinsic voltage-dependent effects and order antiferromagnetically.

Structural diversity, optical and magnetic properties of a series of manganese thioarsenates with 1,10-phenanthroline or 2,2'-bipyridine ligands: using monodentate methylamine as an alkalinity regulator.

The exploration in two hydro(solvo)thermal reaction systems As/S/Mn(2+)/phen/methylamine aqueous solution and As/S/Mn(2+)/2,2'-bipy/H(2)O affords five new manganese thioarsenates with diverse structures, namely, (CH(3)NH(3)){[Mn(phen)(2)](As(V)S(4))}·phen (1 and 1'), (CH(3)NH(3))(2){[Mn(phen)](2)(As(V)S(4))(2)} (2), {[Mn(phen)(2)](As(III)(2)S(4))}(n) (3), {[Mn(phen)](3)(As(III)S(3))(2)}·H(2)O (4), and {[Mn(2,2'-bipy)(2)](2)(As(V)S(4))}[As(III)S(S(5))] (5). Compound 1 comprises a {[Mn(phen)(2)](As(V)S(4))}(-) complex anion, a monoprotonated methylamine cation and a phen molecule. Compound 2 contains a butterfly like {[Mn(phen)](2)(As(V)S(4))(2)}(2-) anion charge compensated by two monoprotonated methylamine cations. Compound 3 is a neutral chain formed by a helical (1)(∞)(As(III)S(2)(-)) vierer chain covalently bonds to [Mn(II)(phen)](2+) complexes via all its terminal S atoms. Compound 4 features a neutral chain showing the stabilization of noncondensed (As(III)S(3))(3-) anions in the coordination of [Mn(II)(phen)](2+) complex cations. Compound 5 features a mixed-valent As(III)/As(V) character and an interesting chalcogenidometalates structure, where a polycation formed by the connection of two [Mn(2,2'-bipy)(2)](2+) complex cation and a (As(V)S(4))(3-) anion acts as a countercation for a polythioarsenate anion, [As(III)S(S(5))](-). The title compounds exhibit optical gaps in the range 1.58-2.48 eV and blue photoluminescence. Interestingly, compound 1 displays a weak second harmonic generation (SHG) response being about 1/21 times of KTP (KTiOPO(4)). Magnetic measurements show paramagnetic behavior for 1 and dominant antiferromagnetic behavior for 2-5. Of particular interest is 4, which is the first manganese chalcogenide showing spin-canting characteristic.

X-Ray crystal structure of [HSm{V(IV)O(TPPS)}]n and encapsulation of nitrogen molecules in 1-D channels.

The crystal structure of an N(2)-encapusulated MOF, which is stable under open-air conditions at ambient temperature, was determined by single-crystal X-ray diffraction at 123 K. The crystal MOF of [HSm{V(IV)O(TPPS)}](n) designed to have 1-D channels periodically constricted by porphyrins planes adsorbed N(2) at 77 K. The adsorbed N(2) molecules remained in the 1-D channels even after warming to ambient temperature. The single-crystal structure of [HSm{V(IV)O(TPPS)}](n)⊃N(2) determined by X-ray diffraction indicated that N(2) molecules trapped in the constricted parts block other N(2) molecules in 1-D channels from escaping from the MOF. Such a unique encapsulation mode provides a promising approach toward designing novel MOFs with high gas storage capacity at ambient temperature.