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A new caesium sodium samarium borate phosphate, CsNa2Sm2(BO3)(PO4)2, has been obtained successfully by the high-temperature solution growth (HTSG) method and single-crystal X-ray diffraction analysis reveals that it crystallizes in the orthorhombic space group Cmcm. The structure contains BO3, PO4, NaO7 and SmO7 polyhedra which are interconnected via corner- or edge-sharing O atoms to form a three-dimensional [Na2Sm2(BO3)(PO4)2]∞ network. This network delimits large cavities where large Cs+ cations reside to form the total structure. Under 402 nm light excitation, CsNa2Sm2(BO3)(PO4)2 exhibits three emission bands due to the 4f→4f transitions of Sm3+. Furthermore, we introduced Gd3+ into Sm3+ sites to optimize the Sm3+ concentration and improve the luminescence intensity. The optimal concentration is Gd/Sm = 98/2. The luminescent lifetime of a series of CsNa2Gd2(1–x)Sm2x(BO3)(PO4)2 phosphors shows a gradual degradation of lifetime from 2.196 to 0.872 ms for x = 0.01–0.10. The Commission Internationale de l'Eclairage (CIE) 1931 calculation reveals that CsNa2Gd1.96Sm0.04(BO3)(PO4)2 can emit orange light under 402 nm excitation.
Supporting information
CCDC reference: 2031718
Data collection: APEX2 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2020).
Caesium disodium disamarium borate bis(phosphate)
top
Crystal data top
CsNa2Sm2(BO3)(PO4)2 | Dx = 4.177 Mg m−3 |
Mr = 728.34 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmcm | Cell parameters from 1320 reflections |
a = 7.0631 (6) Å | θ = 2.3–24.4° |
b = 15.2881 (15) Å | µ = 13.54 mm−1 |
c = 10.725 (1) Å | T = 296 K |
V = 1158.10 (19) Å3 | Block, colorless |
Z = 4 | 0.15 × 0.15 × 0.10 mm |
F(000) = 1296 | |
Data collection top
Bruker SMART APEXII CCD area detector diffractometer | 812 independent reflections |
Radiation source: fine-focus sealed tube | 727 reflections with I > 2σ(I) |
Detector resolution: 83.33 pixels mm-1 | Rint = 0.037 |
ω scans | θmax = 28.3°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | h = −9→4 |
Tmin = 0.158, Tmax = 0.590 | k = −19→19 |
3854 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0233P)2 + 0.2713P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.022 | (Δ/σ)max = 0.001 |
wR(F2) = 0.048 | Δρmax = 1.09 e Å−3 |
S = 1.05 | Δρmin = −1.54 e Å−3 |
812 reflections | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
59 parameters | Extinction coefficient: 0.00072 (6) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. A suitable single crystal with dimensions of 0.15 × 0.15
× 0.05 mm was selected and mounted on a glass fiber for the
single-crystal X-ray diffraction (SC-XRD) experiments. Data collection was
performed using a Bruker Smart Apex2 CCD diffractometer with
graphite-monochromated Mo-Ka (λ = 0.71073 Å) radiation at a
temperature of 293 K. The data set was corrected for Lorentz and polarization
factors and for absorption by applying the ω-scan technique (Bruker,
2017). The structure was solved by direct method and refined by full-matrix
least-squares fitting on F2 by Shelx-2017 (Sheldrick, 2015). The
observed intensities are consistent with an orthorhombic C-centered
space group Cmcm. The final refined solution obtained was checked with the
Addsym algorithm in the program PLATON (Spek, 2020), and no higher symmetry
was found. Crystallographic data and structural refinement were summarized in
Table 1. The atomic coordinates and thermal parameters are given as supporting
information (Table S1, S2), and some important bond distances are summarized
in Table S3. Further details of the crystal structure investigations can be
obtained from the CCDC database on quoting the depository number of 2031718 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cs1 | 0.500000 | 0.48636 (5) | 0.750000 | 0.0370 (2) | |
Na1 | 0.7563 (3) | 0.74620 (18) | 0.750000 | 0.0248 (6) | |
Sm1 | 1.000000 | 0.61983 (2) | 0.52841 (3) | 0.00667 (11) | |
B1 | 1.000000 | 0.5156 (7) | 0.750000 | 0.0109 (19) | |
P1 | 0.500000 | 0.68276 (10) | 0.52246 (13) | 0.0083 (3) | |
O1 | 1.000000 | 0.4772 (3) | 0.6361 (4) | 0.0167 (10) | |
O2 | 1.000000 | 0.6087 (4) | 0.750000 | 0.0183 (14) | |
O3 | 0.500000 | 0.7613 (3) | 0.6133 (4) | 0.0127 (9) | |
O4 | 0.500000 | 0.7240 (3) | 0.3918 (4) | 0.0141 (9) | |
O5 | 0.6758 (4) | 0.62691 (19) | 0.5449 (3) | 0.0196 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.0384 (4) | 0.0263 (4) | 0.0463 (5) | 0.000 | 0.000 | 0.000 |
Na1 | 0.0134 (13) | 0.0473 (19) | 0.0138 (13) | −0.0010 (12) | 0.000 | 0.000 |
Sm1 | 0.00608 (16) | 0.00696 (17) | 0.00696 (17) | 0.000 | 0.000 | −0.00011 (11) |
B1 | 0.008 (4) | 0.023 (5) | 0.002 (4) | 0.000 | 0.000 | 0.000 |
P1 | 0.0050 (7) | 0.0097 (7) | 0.0101 (7) | 0.000 | 0.000 | 0.0016 (6) |
O1 | 0.031 (3) | 0.007 (2) | 0.012 (2) | 0.000 | 0.000 | −0.0042 (17) |
O2 | 0.038 (4) | 0.009 (3) | 0.008 (3) | 0.000 | 0.000 | 0.000 |
O3 | 0.015 (2) | 0.013 (2) | 0.010 (2) | 0.000 | 0.000 | −0.0034 (17) |
O4 | 0.017 (2) | 0.017 (2) | 0.008 (2) | 0.000 | 0.000 | −0.0008 (17) |
O5 | 0.0075 (15) | 0.0171 (17) | 0.034 (2) | 0.0028 (11) | −0.0006 (14) | 0.0071 (14) |
Geometric parameters (Å, º) top
Cs1—O5i | 3.316 (3) | Na1—O5i | 2.913 (4) |
Cs1—O5ii | 3.316 (3) | Sm1—O5x | 2.299 (3) |
Cs1—O5iii | 3.316 (3) | Sm1—O5 | 2.299 (3) |
Cs1—O5 | 3.316 (3) | Sm1—O1xi | 2.305 (4) |
Cs1—O4iv | 3.557 (4) | Sm1—O3ix | 2.369 (4) |
Cs1—O4v | 3.557 (4) | Sm1—O2 | 2.3826 (5) |
Cs1—O1 | 3.7393 (14) | Sm1—O1 | 2.468 (4) |
Cs1—O1vi | 3.7393 (14) | Sm1—O4ix | 2.537 (4) |
Cs1—O1i | 3.7393 (14) | B1—O1 | 1.355 (6) |
Cs1—O1vii | 3.7393 (14) | B1—O1i | 1.355 (6) |
Na1—O3i | 2.341 (3) | B1—O2 | 1.423 (11) |
Na1—O3 | 2.341 (3) | P1—O5 | 1.526 (3) |
Na1—O4viii | 2.342 (3) | P1—O5iii | 1.526 (3) |
Na1—O4ix | 2.342 (3) | P1—O4 | 1.537 (4) |
Na1—O2 | 2.717 (5) | P1—O3 | 1.546 (4) |
Na1—O5 | 2.913 (4) | | |
| | | |
O1—B1—O1i | 128.6 (9) | O5iii—P1—O4 | 111.92 (16) |
O1—B1—O2 | 115.7 (4) | O5—P1—O3 | 109.57 (16) |
O1i—B1—O2 | 115.7 (4) | O5iii—P1—O3 | 109.57 (16) |
O5—P1—O5iii | 108.9 (2) | O4—P1—O3 | 104.8 (2) |
O5—P1—O4 | 111.92 (16) | | |
Symmetry codes: (i) x, y, −z+3/2; (ii) −x+1, y, −z+3/2; (iii) −x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, z+1/2; (vi) x−1, y, z; (vii) x−1, y, −z+3/2; (viii) −x+3/2, −y+3/2, z+1/2; (ix) −x+3/2, −y+3/2, −z+1; (x) −x+2, y, z; (xi) −x+2, −y+1, −z+1. |
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