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Lanthanide (LnIII) ions were successfully chelated and sensitized with a tripodal ligand. The absolute LnIII-centered emission efficiencies were ~3% for both the europium(III) (EuIII) and terbium (TbIII) complexes and up to 54% for the cerium(III) (CeIII) complex. The differences in emission quantum yields for the early lanthanides (CeIII) and the mid lanthanides (EuIII and TbIII) were attributed to their d–f and f–f nature, respectively. Despite the low quantum yield of the EuIII complex, the combination of the residual ligand fluorescence and the red EuIII emission resulted in a bluish-white material with the Commission Internationale de l’Eclairage (CIE) coordinates (0.258, 0.242). Thus, metal complexes of the ligand could be used in the generation of single-component white-light-emitting materials.

Tin halide perovskites and perovskite-related materials have emerged as promising lead-free hybrid materials for various op-toelectronic applications. While remarkable progress has been achieved in...

Binuclear platinum(II) complexes with strong Pt-Pt interactions are an interesting class of luminescent materials, of which photophysical properties could be controlled via multiple ways through organic ligands and Pt-Pt distance. While a number of binuclear platinum(II) complexes have been developed with tunable emissions, achieving high photoluminescence quantum efficiency (PLQE) remains challenging and of great interest. Here we report the synthesis and characterization of a series of binuclear 2,4-difluorophenylpyridine platinum(II) complexes bridged by thiazol-2-thiolate ligands with different bulkiness. The three complexes were found to have short Pt-Pt distances ranging from 2.916 to 2.945 Å. The strong Pt-Pt interactions lead to pronounced metal-metal-to-ligand charge transfer (MMLCT) absorptions between 450 and 500 nm, and strong

The two metal-deficient series of quaternary Ge-containing sulfides RE3M0.5GeS7 (RE = La–Nd, Sm; M = Co, Ni), as well as the related Si-containing sulfide Y3Pd0.5SiS7, were prepared by reactions of the elements at 1050 °C. Single-crystal X-ray diffraction analysis performed on all compounds confirmed noncentrosymmetric hexagonal structures (space group P63, Z =2) with cell parameters in the ranges of a =10.0–10.3 A and c =5.7–5.8 A for RE3Co0.5GeS7 and RE3Ni0.5GeS7, or a =9.7891(3) A and c =5.6840(4) A for Y3Pd0.5SiS7. They are classified as La3Mn0.5SiS7-type structures, with M atoms centred within octahedra (in contrast to La3CuSiS7-type structures in which M atoms occupy trigonal planar sites) and Ge atoms centred within tetrahedra, both types of polyhedra being arranged in one-dimensional stacks aligned along the c-direction. Charge balance requirements dictate half-occupancy of the M sites. However, bond valence sum arguments indicated that the M atoms are somewhat underbonded within these octahedral sites, so that there is evidence that in some compounds, they can also enter the trigonal planar site at low occupancy (~5%). Magnetic measurements on RE3Co0.5GeS7 (RE = Ce, Pr, Sm) revealed paramagnetic behaviour for the Ce and Pr members and apparent antiferromagnetic ordering (TN =14 K) for the Sm member; fitting to the Curie-Weiss law gave effective magnetic moments consistent with the presence of RE3+ and Co2+ species. Band structure calculations on ordered models of La3M0.5GeS7 (M = Co, Ni) showed that the Fermi level cuts through M 3d states in the DOS curve and supported the presence of strong M–S and Ge–S bonding interactions.

A metal-organic cage (termed FJI-C9) based on six square-shaped Cu 2 (CO 2 ) 4 paddle-wheel building units and eight flexible 1,3,5-trimethyl-2,4,6-tris(3-phenoxymethyl)benzoic acid (TTBA) linkers has been constructed. The porous FJI-C9 containing large cage of 1.5 nm shows high CO 2 adsorption uptake.

The selenide Ba4Ga4GeSe12, synthesized by reaction of BaSe, Ga2Se3, and GeSe2 at 1173 K, adopts a noncentrosymmetric tetragonal structure (space group P 4 ¯ 2 1 c , Z=2, a=13.5468(4) A, c=6.4915(2) A) consisting of a three-dimensional network built from two types of corner-sharing MSe4 tetrahedra, with Ba cations occupying the intervening voids. It is isostructural to Pb4Ga4GeS12, Pb4Ga4GeSe12, and Ba4Ga4SnSe12, but differs subtly in site ordering. Structural refinements and bond valence sum analysis suggest partial disorder manifested by mixing of 0.75 Ga and 0.25 Ge within one tetrahedral site, and occupation of exclusively Ga within the other tetrahedral site. The optical band gap of 2.18(2) eV, measured from the UV/VIS/NIR diffuse reflectance spectrum, agrees with a calculated gap of 2.35 eV between valence and conduction bands and is consistent with the orange-yellow color of the crystals. Nonlinear optical measurements on powder samples revealed a weak second harmonic generation signal using 2.09 µm as the fundamental laser wavelength.

The ternary selenide Ba4Ga2Se8 has been synthesized by reaction of BaSe, Ga2Se3, and Se at 1023 K. Single-crystal X-ray diffraction analysis revealed a monoclinic structure (space group P21/c, Z=4, a=13.2393(5) A, b=6.4305(2) A, c=20.6432(8) A, β=104.3148(6)°) featuring one-dimensional chains of corner-sharing Ga-centered tetrahedra and discrete S e 2 2 − anionic units, with charge-compensating Ba2+ cations located between them. The UV/vis/NIR diffuse reflectance spectrum reveals an optical band gap of 1.63(2) eV, which is consistent with the black color of the crystals and agrees with a calculated gap of 1.51 eV obtained from band structure calculations. The presence of the S e 2 2 − units narrows the band gap in Ba4Ga2Se8 relative to other Ba–Ga–Se phases.

The quaternary rare-earth chalcogenides RE 3 CuGaS 7 and RE 3 CuGaSe 7 ( RE =La–Nd) have been prepared by reactions of the elements at 1050 °C and 900 °C, respectively. They crystallize in the noncentrosymmetric La 3 CuSiS 7 -type structure (hexagonal, space group P 6 3 , Z =2) in which the a -parameter is largely controlled by the RE component ( a =10.0–10.3 A for the sulfides and 10.3–10.6 A for the selenides) whereas the c -parameter is essentially fixed by the choice of Ga and chalcogen atoms within tetrahedral units ( c =6.1 A for the sulfides and 6.4 A for the selenides). They extend the series RE 3 M Ga Ch 7 , previously known for divalent metal atoms ( M =Mn–Ni), differing in that the Cu atoms in RE 3 CuGa Ch 7 occupy trigonal planar sites instead of octahedral sites. Among quaternary chalcogenides RE 3 MM ′ Ch 7 , the combination of monovalent ( M =Cu) and trivalent ( M ′=Ga) metals is unusual because it appears to violate the condition of charge balance satisfied by most La 3 CuSiS 7 -type compounds. The possibility of divalent Cu atoms was ruled out by bond valence sum analysis, magnetic measurements, and X-ray photoelectron spectroscopy. The electron deficiency in RE 3 CuGa Ch 7 is accommodated through S-based holes at the top of the valence band, as shown by band structure calculations on La 3 CuGaS 7 . An optical band gap of about 2.0 eV was found for La 3 CuGaSe 7 .

A homologous series of ternary rare-earth zinc arsenides, prepared by reactions of the elements at 750 °C, has been identified with the formula RE(2-y)Zn4As4·n(REAs) (n = 2, 3, 4) for various RE members. They adopt trigonal structures: RE(4-y)Zn4As6 (RE = La-Nd), space group R3m1, Z = 3; RE(5-y)Zn4As7 (RE = Pr, Nd, Sm, Gd), space group P3m1, Z = 1; RE(6-y)Zn4As8 (RE = La-Nd, Sm, Gd), space group R3m1, Z = 3. The Zn atoms can be partially substituted by Mn atoms, resulting in quaternary derivatives RE(2-y)Mn(x)Zn(4-x)As4·n(REAs). Single-crystal structures were determined for nine ternary and quaternary arsenides RE(2-y)M4As4·n(REAs) (M = Mn, Zn) as representative examples of these series. The structures are built by stacking close-packed nets of As atoms, sometimes in very long sequences, with RE atoms occupying octahedral sites and M atoms occupying tetrahedral sites, resulting in an intergrowth of [REAs] and [M2As2] slabs. The recurring feature of all members of the homologous series is a sandwich of [M2As2]-[REAs]-[M2As2] slabs, while rocksalt-type blocks of [REAs] increase in thickness between these sandwiches with higher n. Similar to the previously known related homologous series REM(2-x)As2·n(REAs) which is deficient in M, this new series RE(2-y)M4As4·n(REAs) exhibits deficiencies in RE to reduce the electron excess that would be present in the fully stoichiometric formulas. Enthalpic and entropic factors are considered to account for the differences in site deficiencies in these two homologous series. Band structure calculations indicate that the semiconducting behaviour of the parent n = 0 member (with CaAl2Si2-type structure) gradually evolves, through a narrowing of the gap between valence and conduction bands, to semimetallic behaviour as the number of [REAs] blocks increases, to the limit of n = ∞ for rocksalt-type REAs.

The nonlinear optical (NLO) BaGa 4 S 7 polycrystalline materials with stoichiometric composition were synthesized from BaS, Ga, and S via solid-state reactions in the dual temperature zone rocking furnace with excess sulfur, and crystal BaGa 4 S 7 for the mid-infrared (IR) was grown with Bridgman–Stockbarger technique. The ultraviolet (UV) and IR optical absorption edges of crystal BaGa 4 S 7 were found to be at 350 nm and 13.7 μm, respectively. Its thermal conductivities at 50 °C were 1.45 W/(m K), 1.58 W/(m K) and 1.68 W/(m K) along a -, b - and c -directions, respectively. The laser damage threshold of a single crystal was about 7.1 J/cm 2 at 2.1 μm, and 26.2 J/cm 2 at 9.58 μm. The idler non-critical phase-matching OPO wavelength was between 6 and 10 μm when the pumped wavelength was varied around 2.2 μm.

Two series of Mn-substituted rare-earth zinc arsenides RE(1-y)Mn(x)Zn(2-x)As2 (RE = Eu-Lu) and RE(2-y)Mn(x)Zn(4-x)As4 (RE = La-Nd, Sm, Gd) were prepared by reaction of the elements at 750 °C. Both series are derived from ideal empirical formula REM2As2 (M = Mn, Zn) and adopt crystal structures related to the trigonal CaAl2Si2-type (space group P3m1) in which hexagonal nets of RE atoms and [M2As2] slabs built up of edge-sharing M-centered tetrahedra are alternately stacked along the c-direction. For compounds with divalent RE components (Eu, Yb), the fully stoichiometric and charge-balanced formula REM2As2 is obtained, with Mn and Zn atoms statistically disordered within the same tetrahedral site. For compounds with trivalent RE components, the RE sites become deficient, and the Mn atoms are segregated from the Zn atoms in separate tetrahedral sites. Within the series RE(1-y)Mn(x)Zn(2-x)As2 (Gd-Tm, Lu), the parent CaAl2Si2-type structure is retained, and the Mn atoms are disordered within partially occupied interstitial sites above and below [Zn(2-x)As2] slabs. Within the series RE(2-y)Mn(x)Zn(4-x)As4 (RE = La-Nd, Sm, Gd), the c-axis becomes doubled as a result of partial ordering of Mn atoms between every other pair of [Zn(2-x)As2] slabs. Attempts to synthesize Gd-containing solid solutions with the charge-balanced formula Gd0.67Mn(x)Zn(2-x)As2 suggested that these phases could be formed with up to 50% Mn substitution. Band structure calculations reveal that a hypothetical superstructure model with the formula La1.33MnZn3As4 would have no gap at the Fermi level and that slightly lowering the electron count alleviates antibonding Mn-As interactions; a spin-polarized calculation predicts nearly ferromagnetic half-metallic behavior. X-ray photoelectron spectroscopy confirms the presence of divalent Mn in these compounds.

Four series of ternary rare-earth zinc arsenides have been prepared by reaction of the elements at 750 °C: RE4Zn(2-x)As5 forming for RE = La-Nd, Sm; and RE5Zn(2-x)As6, RE6Zn(2-x)As7, RE7Zn(2-x)As8 forming for RE = Ce, Pr, Nd, Sm. They crystallize in trigonal structure types in space group P3m1 with Z = 1 for RE4Zn(2-x)As5 and RE7Zn(2-x)As8, or space group R3m1 with Z = 3 for RE5Zn(2-x)As6 and RE6Zn(2-x)As7. Through the structural principle of intergrowing rocksalt-type [REAs] slabs of variable thickness within a parent CaAl2Si2-type structure containing Zn-deficient [Zn(2-x)As2] slabs built from edge-sharing Zn-centered tetrahedra, these ternary arsenides belong to a homologous series with the formulation REZn(2-x)As2·n(REAs) (n = 3, 4, 5, 6). Quaternary derivatives Ce4(Mn,Zn)(2-x)As5 and Ce6(Mn,Zn)(2-x)As7 were also obtained in which Mn partially substitutes for Zn. Band structure calculations predict that the electronic properties can be gradually modified from semiconducting to semimetallic behavior as more [REAs] slabs are introduced.

The ternary rare-earth zinc arsenides RE Zn 2 As 3 ( RE =La–Pr) have been prepared by reactions of the elements at 800 °C. They adopt new tetragonal structure types, with the La member (space group I 4/ mmm , Z =4, a =4.1133(2) A, c =32.1246(14) A) differing from the Ce and Pr members (space group P 4/ nmm , Z =2, a =4.0804(6)–4.0534(12) A, c =16.089(5)–16.059(10) A, respectively) in the disposition of RE -centred square antiprisms on opposite sides of square As nets. The structures contain thick anionic slabs, built from edge-sharing ZnAs 4 tetrahedra, that can be considered either as stackings of three PbO-type layers or as fragments of the fluorite-type structure. These slabs are deficient in Zn and are reminiscent of the same features in binary arsenide Zn 3 As 2 . LaZn 2 As 3 exhibits temperature-independent paramagnetism whereas CeZn 2 As 3 follows modified Curie–Weiss behavior consistent with Ce 3+ species but with no occurrence of long-range ordering.

Eight new quaternary chalcogenides BaRE2In2Ch7 (RE = La–Nd; Ch = S, Se) have been prepared by reactions of BaCh, In2Ch3, RE, and Ch at high temperatures. They adopt orthorhombic structures (space group Pbam, Z = 2; a = 11.6300(8)–11.5895(7) A, b = 12.4202(9)–12.3001(8) A, c = 4.0689(3)–4.0028(2) A for the sulfides; a = 12.1515(6)–12.1358(10) A, b = 12.9367(7)–12.8510(11) A, c = 4.1966(2)–4.1363(4) A for the selenides) containing one-dimensional anionic [In2Ch7] ribbons of corner-sharing InCh5 trigonal bipyramids, separated by Ba and RE cations. The structure is an ordered variant of the rare Eu3Sn2S7-type with Ba atoms occupying larger sites with nearly cubic geometry and RE atoms occupying smaller sites with bicapped trigonal prismatic geometry. The InCh5 trigonal bipyramids, which are unusual, exhibit four shorter In–Ch bonds and a fifth longer one. Band structure calculations indicate that BaLa2In2S7 is a direct gap semiconductor, and corroborate the description of the In coordination as CN4 + 1. On the basis of the optical absorption spectra, band gaps were estimated to be 1.87(2) eV for BaLa2In2S7 and 1.66(2) eV for BaLa2In2Se7.

New middle infrared nonlinear optical crystals of BaGa{sub 2}GeX{sub 6}(X=S, Se) have been synthesized. The structures of both BaGa{sub 2}GeS{sub 6} and BaGa{sub 2}GeSe{sub 6} were found to be isomorphous exhibiting a three-dimensional framework constructed by the parallel alignment of Ga or Ge tetrahedron groups along the c-aix. The ultraviolet transmittance spectrum indicates the short-wavelength absorption edges of BaGa{sub 2}GeS{sub 6} and BaGa{sub 2}GeSe{sub 6} are 380 nm and 440 nm, respectively. The IR transmittance spectrum shows that the absorption edge of the BaGa{sub 2}GeS{sub 6} crystal is 13.7 {mu}m. Second-harmonic generation of the powder samples was measured with a 2.05 {mu}m laser using the Kurtz and Perry technique, which showed that BaGa{sub 2}GeS{sub 6} and BaGa{sub 2}GeSe{sub 6} are phase-matched materials, and their measured SHG coefficient is {approx}2.1 and {approx}3.5 times as large as the coefficient of AgGaS{sub 2}, or 26.3 pm/V and 43.7 pm/V. - Graphical abstract: The structure of BGGS viewed along the a and c axis and an as-grown crystal. Highlights: Black-Right-Pointing-Pointer Mid-IR NLO crystals of BaGa{sub 2}GeX{sub 6}(X=S, Se) with wide band-gap have been discovered. Black-Right-Pointing-Pointer The structures were constructed by the parallel alignment of Ga or Ge tetrahedra. Black-Right-Pointing-Pointer They are phase-matchable material withmore » their SHG coefficient of 26.3 and 43.7 pm/V.« less

Well-dispersed palladium nanoparticles (Pd NPs) supported on amine-functionalized, mixed-linker metal–organic frameworks (MIXMOFs) based on MIL-53(Al) were prepared by using the ion-exchange method. Pd NPs were characterized by powder X-ray diffraction (XRD), N2 adsorption, transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The mean diameter of Pd NPs is approximately 3.2 nm. It was found that the Pd NPs supported on amine-functionalized MIXMOFs are stable at high temperature. The Pd NPs exhibit efficient catalytic activity for Heck reaction and can be easily recovered and reused.

The synthesis of a series of thienyl-substituted pyridinium salts with different counter-anions and their second-order nonlinear optical (NLO) properties are described. Kurtz powder tests revealed that, out of the twelve new pyridinium salts, four possess noncentrosymmetric structures and the maximum powder second harmonic generation (SHG) efficiency is 0.6 times of DAST. Single crystals of three new salts were successfully obtained from methanol by slow evaporation method. X-Ray studies exhibited that they crystallized in the monoclinic space groupP21/c, P21, and P21/n, respectively. (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium 4-hydroxybenzenesulfonate (3c) forms a hydrated noncentrosymmetric phase with a large macroscopic optical nonlinearity 0.5 times of that of DAST at the non-resonant wavelength of λ = 2109 nm, while both (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium 2-amino-3,5-dimethylbenzenesulfonate (3i) and (E)-4-(2-(5-(dimethylamino)thiophen-2-yl)vinyl)-1-methylpyridinium iodide (3a) crystallize in centrosymmetric structures.

A new series of alkaline-alkaline earth fluoride carbonates (KSrCO(3)F, RbSrCO(3)F, KCaCO(3)F, RbCaCO(3)F, CsCaCO(3)F, and Cs(3)Ba(4)(CO(3))(3)F(5)) were synthesized by spontaneous crystallization with molten fluxes. Their crystal structures, except for Cs(3)Ba(4)(CO(3))(3)F(5), exhibit the stacking of [AF](∞) (A = K, Rb, Cs) and [B(CO(3))](∞) (B = Ca, Sr) layers, and the coplanar alignment of [CO(3)] triangles. The results from the UV-vis diffuse reflectance spectroscopy study of the powder samples indicated that the short-wavelength absorption edges were all below 200 nm, except for Cs(3)Ba(4)(CO(3))(3)F(5), which is about 210 nm. Second-harmonic generation (SHG) on polycrystalline samples was measured using the Kurtz and Perry technique, which indicated that these carbonates are all phase-matchable materials in both visible and the UV region, and their measured SHG coefficients were about 3.33, 3.33, 3.61, 1.11, 1.11, and 1.20 times as large as that of d(36) (KDP), respectively.

Three new organic–inorganic supramolecular hybrids, namely, [4,4′-Hbpy]2[HPW12O40]·H2O (4,4′-bpy = 4,4′-bipyridine, 1), [4,4′-H2bpy]6[P2W18O62]2·6H2O (2), [4,4′-H2bpy]5[HP2W18O62]2 (3), were hydrothermally synthesized in situ at different pH. Single crystal X-ray diffraction analyses show that complex 1 constructed from Keggin polyoxoanions and 4,4′-bipyridine organic ligands, exhibits an extended three-dimensional supramolecular network via hydrogen bonding, while 3D supramolecular network of complexes 2–3 were based on Wells–Dawson polyoxoanions and 4,4′-bipyridine organic ligands. The structural differences of complexes 1–3 indicated that the self-assembly process is pH-dependent. Complexes 1–3 have good photocatalytic activity for the photodegradation of methyl orange in the presence of H2O2 under UV light irradiation.

Two new pillared-layer frameworks have been obtained through self-assembly of 4,4′-azobenzene dicarboxylatic acid (4,4′-H2ABDC), oxalate, hydroxyl and LnCl3(Ln = Sm, Eu) under hydrothermal environment and characterized by TGA, IR spectroscopy, element analyses, and X-ray single crystal diffraction. The X-ray structure analyses reveal that the oxalates link the Ln(III) to form metal layers, and 4,4′-ABDC ligands work as pillars to connect adjacent layers to further extend into 3D frameworks. Their magnetic studies show that the two compounds have typical anti-ferromagnetic behaviors.

The title compounds are prepared from the elements in the presence of Ga flux (fused silica tubes, 800 °C for 3 d, 1050 °C for 2 d) and characterized by powder and single crystal XRD.

Ca x Gd 1− x VO 4 crystals were grown by the Czochralski technique. X-ray diffraction analysis showed that as-grown crystals have a zircon-type structure belonging to the tetragonal system. The Ca 2+ -doped concentration was measured by ICP spectroscopy. It was found that the segregation coefficient of the Ca 2+ ion ( k Ca ) decreased with increasing Ca 2+ concentration. XPS experiments validated that V atoms remained pentavalent in Ca x Gd 1− x VO 4 crystals. The Raman spectra of Ca x Gd 1− x VO 4 crystals were investigated at room temperature. The results indicated that the Raman line intensity at about 885 cm −1 increased exponentially with the increase of Ca 2+ concentration. The Ca 2+ dopant influenced the Raman property of GdVO 4 single crystals.

A study was made on effect of niobium on the GdVO4 crystal structure. Yb:GdV0.995Nb0.005O4 crystals were grown by the Czochralski method, and their transmission spectra, absorption spectra, and fluorescence spectra were measured. The GdV0.995Nb0.005O4 crystals acting as new laser host crystals do not affect the absorption of Yb3+. Some spectrum parameters calculated by the Fuchbauer—Ladenburger method indicate that doping of Nb5+ in the GdVO4 crystal improves the spectroscopic properties of Yb3+.

The materials synthesis of polycrystalline of Yb3+: BaWO4 by the way of liquid-phase reaction, and the raw materials of synthesis were detected with ultraviolet spectrum and X-ray powder diffraction method. The colorless and un-cracked Yb3+: BaWO4 crystal was grown by Czochralski method for the first time. The growth condition and annealing technology was investigated. The transmission and absorption spectra of Yb3+: BaWO4 was measured. The result indicates that BaWO4 can be laser host material.

GdVO 4 single crystal co-doped with Nd 3+ and Yb 3+ was grown by the Czochralski method. The X-ray powder diffraction pattern of Nd, Yb: GdVO 4 crystal confirms that the as-grown crystal is isostructural with pure GdVO 4 crystal, and the result of the optical-homogeneity measurement shows that this crystal is comparatively optic homogeneous. Its polarized absorption spectrum and polarized luminescence spectrum were measured at room temperature. The spectrum properties of Nd 3+ and Yb 3+ in Nd,Yb:GdVO 4 crystal are analyzed by the Judd–Ofelt theory and the reciprocity method respectively. And energy transfer between Nd 3+ and Yb 3+ is also discussed.

Tetragonal zircon-type YP 0.1 V 0.9 O 4 single crystal has been pulled using the Czochraski method from YVO 4 –YPO 4 solid-phase system with pulling rate in the 1.5–1.8 mm/h range and the rotation rate at 10–15 r/min. The analytic result for the concentration of P element indicates that YP 0.1 V 0.9 O 4 single crystal can be grown with stoichiometric compositions. The refractive index and the crystal lattice parameters were tested. The optical quality of YP 0.1 V 0.9 O 4 crystal including the optical uniformity and the optical damage threshold was tested and identified.

The title compounds are prepared by solid state reaction of BaS, Ga, Ge, and S or Se (700 °C for 70 h and 1000 °C for 3 d).

KSrCO3F, RbSrCO3F, KCaCO3F, RbCaCO3F, CsCaCO3F, and Cs3Ba4(CO3)3F5 are obtained by spontaneous crystallization from molten mixtures of BCO3 (B: Ca, Sr, Ba) and A2CO3/BF2 (A: K, Rb, Cs).