Structural Diversity, Magnetic Properties, and Luminescent Sensing of

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Structural Diversity, Magnetic Properties, Luminescent Sensing of Flexible Tripodal Ligand of 1,3,5–Tris(4– carbonylphenyloxy)benzene Based Mn(II)/Cd(II) Coordination Polymers Jie Zhang, Liangqin Huo, Xiaoqing Wang, Kegong Fang, Liming Fan, and Tuo-Ping Hu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00986 • Publication Date (Web): 27 Sep 2017 Downloaded from http://pubs.acs.org on September 28, 2017

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Crystal Growth & Design

Structural Diversity, Magnetic Properties, Luminescent Sensing of Flexible Tripodal Ligand of 1,3,5–Tris(4–carbonylphenyloxy)benzene Based Mn(II)/Cd(II) Coordination Polymers Jie Zhang,† Liangqin Huo,† Xiaoqing Wang,† Kegong Fang,‡ Liming Fan,*† and Tuoping Hu*†‡

5 †Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China.

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030051, China. ‡

Supporting Information Placeholder ABSTRACT:

Four

3D

Cd(II)/Mn(II)

coordination polymers, namely, {[Mn1.5(TCPB)(H2O)(μ2 –OH 2 )]·H2O}n (1), (2), [Mn1.5(TCPB)(bib)0.5(DMF)]n (3), and {[Cd2(TCPB)(HCOO)(bib) (H2O)]·0.5Dioxane}n (4), have been constructed from the flexible tripodal ligand of 1,3,5–tris(4–carbonylphenyloxy)benzene (H 3TCPB) with or without the help of bib auxiliary linker (bib=1,4–bis(imidazol–1–yl)benzene). Based on the 1D rod–like {Mn 3 (COO) 8 (μ2 –H 2O) 2 }n SBUs, complex 1 displays a 3D (4,8)–connected flu net with the point symbol of {4 12 .6 12 .8 4}{4 6} 2. Complex 2 shows a novel 3D 12–connected {3 12 .440 .5 12 .6 2 } net based on the 1D {Cd 6(COO) 12 (μ3–OH)2 (μ2 –OH 2) 2 }n SBUs. When 15 the bib bridging ancillary linker was introduced, a trinuclear {Mn 3 (COO) 6} SBUs based 2–fold interpenetrated 3D (3,8)–connected {4 3} 2 {4 6 .6 18 .8 4}–tfz–d net for 3, and a binuclear {Cd 2(COO) 3} SBUs based 3D (3,7)–connected {4.6 2 }{4 7 .6 14 } net with interesting self–penetrating features for 4 were obtained. Variable–temperature magnetic susceptibilities of 1 and 3 have been investigated. The results display the antiferromagnetic exchange interactions between the adjacent Mn II ions of the SBUs in 1 and 3. Fluorescence measurements show 2 and 4 have highly selective and sensitive detection for 20 Cr3+ cations in aqueous solution and nitrobenzene derivatives in DMF.

10 {[Cd3.5(TCPB)2(H2O)3(μ2 –OH 2 )(μ3 –OH)]·H2 O}n

INTRODUCTION

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without the help of bib auxiliary linker. Herein, four 3D CPs with diverse SBUs have been constructed, with the Functional coordination polymers (CPs), as one of the most structures ranging from 3D (4,8)–connected flu net (1), 3D important components of the inorganic–organic hybird 12–connected {312.440.512.62} net (2), 2–fold interpenetrated 3D materials, have drawn more and more attentions for their 55 (3,8)–connected tfz–d net (3), to 3D (3,7)–connected interesting self–assembly modular structures and gigantic {4.62}{47.614} net (4). Besides, magnetic measurements potential applications in the fields of single molecular indicate that 1 and 3 have the antiferromagnetic exchange magnet(SMM), molecule sensing and fluorescent probe, interactions between the adjacent MnII ions of the SBUs. catalysis and photocatalysis, molecular switch, electronic Moreover, the fluorescent measurements show 2 and 4 device, etc.1–10 As we all known, the method of organic 60 exhibit highly selective and sensitive detection for Cr3+ linkers connected metal ions to form such materials, will cations and nitrobenzene derivatives. deeply affect those properties and applications.11–15 Thus, the strategy of building functional CPs through rational choice Experimental Section and design of organic linkers has proved to be an efficient 16–19 routine. Materials and General Methods. All the reagents were Benefit from the flexible backbones and more freedom in commercially obtained, and used directly. And the the process of coordinating with metal ions, the flexible 65 instrument as well as the test conditions are the same as ligands have been widely selected in the building of those of the references unless specifically mentioned.37,38 functional CPs.20–26 It is noteworthy that CPs based on the Preparation of {[Mn1.5(TCPB)(H2O)(μ2–OH2)]·H2O}n (1). flexible ligands exhibit breathtaking crystal structural A mixture of H3TCPB (0.004 mmol, 1.9 mg), MnCl2·4H2O transformations in the solid state, which were known as (0.008 mmol, 1.6 mg), and 1 mL DMF:H2O solution (v/v = 1/1) single crystal to single crystal (SC–SC) transformation.27–30 70 was added to a glass tube, then pumped to a near–vacuum, Moreover, such CPs show interesting “breathing effects” heated at 95°C for 3000 minutes, and cooled to 25°C with a sometimes, which may greatly improve the performances of cooling rate of 5 oC/h. Colorless block crystals of 1 were CPs in terms of adsorption and separation, sensing, and obtained with the yield of ca. 46% (based on H3TCPB). Anal. shape memory.31–34 Thus, the design of flexible ligands is very Calcd for C54H38Mn3O24: C, 52.48; H, 3.10 (%). Found: C, 51.97; meaningful and can generate functional CPs with highly 75 H, 3.21 (%). IR (cm–1, KBr): 3465 (m), 2363 (m), 1595 (vs), 1542 selective adsorption and sensing for molecules.35,36 (s), 1404 (s), 1232 (s), 1160 (s), 1113 (m), 1001 (m), 875 (m), 777 Inspired by above considerations, we design four CPs by (s), 625 (m), 534 (w). selecting the flexible tripodal ligand of 1,3,5–tris(4–carbonylphenyloxy)benzene (H3TCPB) with or

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Preparation of {[Cd3.5(TCPB)2(H2O)3(μ2–OH2)(μ3–OH)]·H2O}n (2). A mixture of H3TCPB (0.004 mmol, 1.9 mg), Cd(NO3)2·4H2O (0.008 mmol, 2.5 mg), and 1 mL mixed solution of DMF:ETOH:H2O (v/v/v = 1/1/2) was added to a hard glass tube, pumped to a near–vacuum, heated at 120°C for 50 h, and cooled to 25°C with a decreasing rate of 2 oC/h. Colorless block crystals of 2 were obtained with the yield of ca. 63% (based on H3TCPB). Anal. Calcd for C108H80Cd7O47: C, 44.47; H, 2.76 (%). Found: C, 44.79; H, 2.79 (%). IR (cm–1, KBr): 3441 (m), 1599 (vs), 1540 (s), 1496 (m), 1455 (m), 1397 (vs), 1235 (s), 1162 (m), 1118 (m), 1001 (s), 872 (m), 781 (s), 626 (m), 534 (w). Preparation of [Mn1.5(TCPB)(bib)0.5(DMF)]n (3). The mixture of H3TCPB (0.004 mmol, 1.9 mg), bib (0.008 mmol, 1.7 mg), MnCl2·4H2O (0.008 mmol, 1.6 mg), and 1 mL DMF:Dioxane:H2O (v/v/v = 1/1/2) was added to a glass tube, heated at 120°C for 50 h, and then cooled to 25 °C with a falling rate of 2 oC/h. Light yellow block crystals of 3 were obtained with the yield of ca. 57% (based on H3TCPB). Anal. Calcd for C72H54Mn3N6O20: C, 58.11; H, 3.66; N, 5.65 (%). Found: C,58.39; H, 3.76; N, 5.59 (%). IR (cm–1, KBr): 3407 (m), 1663 (m), 1596 (vs), 1499 (m), 1397 (vs), 1221 (vs), 1162 (m), 1118 (m), 1062 (m), 1006 (s), 834 (s), 784 (vs),711 (m), 652 (m), 541 (w). Preparation of {[Cd2(TCPB)(HCOO)(bib)(H2O)]·0.5Dioxane}n (4). The synthesis process of 4 is similar with that of 3 except that the MnCl2·4H2O was replaced by Cd(NO3)2·4H2O. Faint yellow block crystals of 4 were achieved with the yield of ca. 51% (based on H3TCPB). Anal. Calcd for C42H32Cd2N4O13: C, 49.19; H, 3.15; N, 5.46 (%). Found: C,49.32; H, 3.31; N, 5.38 (%). IR (cm–1, KBr): 3426 (m), 1593 (vs), 1528 (s), 1461 (m), 1394 (vs), 1303 (m), 1224 (vs), 1159 (m), 1110 (m), 1065 (m), 1016 (m), 966 (w), 837 (m), 784 (m), 737 (w), 649 (m), 532 (w). X–ray crystallography. Single–crystal data of complexes 1–4 were collected on a Siemens SMART diffractometer with graphite–monochromatized Mo–Kα radiation (λ = 0.71073 Å). Empirical absorption corrections and Lorentz polarization were applied. Those structures were resolved by direct methods with SHELXS–97 and refined by full–matrix least–squares methods on F2 by using the package of SHELXTL–97.39, 40 For 3, the disorder atoms (C34–C36, and N3) of the coordinated DMF molecules were refined with split positions and an occupancy ratio of 58.9:41.1. In complex 4, two disordered atoms of the formates (C14, and

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O5) were refined as 3 with an occupancy ratio being 45:55. Detailed crystallographic data and structural refinements of complexes 1–4 were gathered in Table S1. Table S2 presents the selected angles and bond distances for complexes 1–4. 50 Further details on the crystal structure investigations of the title complexes can be obtained from http://www.ccdc.cam.ac.uk/ by quoting the depository number CCDC–1562146–1562149 for 1–4, respectively. RESULT AND DISCUSSION

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Structural Description of {[Mn1.5(TCPB)(H2O)(μ2–OH2)]·H2O}n (1). Although this CPs and its photoluminescence have been reported by Liu and co–workers,41 we systematically studied the structure and magnetic property of 1 here. Complex 1 crystallizes in 60 triclinic system with space group Pī. As can been seen form Figure 1, there are one and a half of crystallographically independent MnII cations, one TCPB3– ligand, one μ2–coordinated water molecule, one coordinated water molecule, and one lattice water molecule in the asymmetric 65 unit of 1. And Mn1 is centrosymmetric and surrounded by four carboxyl oxygen atoms (O1, and O11) and two μ2–H2O, leaving a distorted {MnO6} octahedral geometry. While Mn2 is located in a distorted {MnO6} octahedral coordination geometry, linked by four carboxyl oxygen atoms (O8, O2D, 70 O5E, and O5F), one μ2–coordinated water molecule (O9), and one H2O molecule (O10). Besides, the Mn–O bond lengths are in the range of 2.070(1)–2.311(3) Å.

Figure 1. The asymmetric unit of 1 (Symmetry codes: A: 1–x, 2–y, –z;

75 B: 1–x, 2–y, 1–z; C: x, y, –1+z; D: x, y, 1+z; E: –1+x, y, z; F: 1–x, 1–y, 2–z.).

Figure 2. The 1D rod–like {Mn3(COO)8(μ2–H2O)2}n SBUs.

Figure 3. (a) The 3D framework of 1. (b) The 2–nodal (4,8)–connected 3D flu net with the point symbol of {412.612.84}{46}2 for 1 (pale blue

80 spheres: trinuclear {Mn3(COO)8(μ2–H2O)2} SBUs, dark red spheres: TCPB3– ligands.).


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Scheme 1. Coordination modes of TCPB3– in 1–4.

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In the formation of 1, the H3TCPB ligand is completely deprotonated and adopts (κ0–κ2)–(κ1–κ1)–(κ1–κ1)–μ6 coordination mode (Mode I, see Scheme 1), with the dihedral angles of α, β, γ, δ, ε, and ζ (α, β, γ, δ, ε, and ζ correspond to 65 the dihedral angles between rings A/B, A/C, A/D, B/C, B/D, and C/D, details seen Scheme 1 and Table 1&2) being 83.93°, 49.63°, 10.03°, 55.15°, 89.62°, and 50.05°, respectively. The bridging μ2–η1:η1 carboxyl groups cooperated with the bridging μ2–η2 carboxyl groups of the TCPB3– ligands as well 70 as the μ2–coordinated water molecule, successfully forming an interesting 1D rod–like {Mn3(COO)8(μ2–H2O)2}n SBUs, in which the Mn···Mn distances being 3.663 Å (Mn1···Mn2C), 3.507 Å (Mn2···Mn2H, Symmetry code: H: –x, 1–y, 2–z.) (Figure 2). The μ6–TCPB3– ligands connected the 1D rod–like 75 {Mn3(COO)8(μ2–H2O)2}n SBUs to construct a 3D framework finally (Figure 3a). Topological analysis shows that complex 1 is a 2–nodal 4,8–connected net with stoichiometry of (4–c)2(8–c), where the TCPB3– ligands and the trinuclear {Mn3(COO)8(μ2–H2O)2} 80 SBUs (Figure S1) are regarded as 4–connectd and 8–connected nodes, respectively (Figure 3b and Figure S2). Thus, the point symbol of 1 is {412.612.84}{46}2, with the topological type being flu/fluorite; sqc169 (topos&RCSR.ttd).42–45 Structural Description of {[Cd3.5(TCPB)2(H2O)3(μ2–OH2)(μ3–OH)]·H2O}n (2). Complex 2 crystallizes in monoclinic system C2/c. And the asymmetric unit consists of three and a half of CdII cations, two TCPB3– ligands, three coordinated H2O molecules, one μ2–coordinated water molecule, one μ3–OH–, and one H2O molecule. As can be seen in Figure 4, there are four different CdII ions with interesting coordination geometry. Cd1 and Cd4 are located in the similar distorted {CdO6} octahedron geometry, completed by four carboxyl oxygen atoms, one μ3–OH–, and one coordinated H2O molecule (μ2–coordinated 85 H2O for Cd4). Cd2 lies in a fascinating {CdO6} wedge–shaped coordination geometry, which has the rotation symmetry axis of L2, surrounded by four carboxyl oxygen atoms (O10, O11, O10D, and O11D), and two coordinated water molecules (O12, and O12D). Cd3 is seven coordinated and linked by four carboxyl oxygen atoms (O15, O7H, O22I, and O23I), one μ3–OH– (O5H), one μ2–coordinated water molecule (O4G), and one H2O molecule (O16), exhibiting a pentagonal bipyramid

coordination geometry. Besides, the bond lengths of Cd–O are in the range of 2.188(8)–2.621(7) Å. The H3TCPB ligand is partly deprotonated in the assembly of 2, it adopts two distinct coordination modes of (κ1–κ1)–(κ1–κ0)–(κ1–κ2)–μ5 (Mode II, with the dihedral angles of α, β, γ, δ, ε, and ζ being 69.95°, 49.48°, 71.64°, 68.67°, 72.22°, and 32.43°) vs (κ1–κ2)–(κ2–κ1)–(κ1–κ1)–μ7 (Mode III, with the dihedral angles of α, β, γ, δ, ε, and ζ being 58.11°, 71.07°, 88.45°, 70.35°, 74.06°, and 35.62°). It is noteworthy that the bridging μ2–η1:η1 and the bridging+chelating μ3–η2:η1 of the Mode II TCPB3– ligand, the bridging μ3–η2:η1 carboxyl groups of the Mode III TCPB3– ligand, the μ2–coordinated H2O, as well as the μ3–OH– anions cooperated with each other to bridge Cd1, Cd3, and Cd4 ions, successfully forming a novel 1D {Cd6(COO)12(μ3–OH)2(μ2–OH2)2}n SBUs (Figure 5),46 in which the nearest Cd···Cd distances are 3.701 Å for Cd1···Cd4B, 4.139 Å for Cd1···Cd3C, 3.726 Å for Cd4···Cd3F, 3.960 Å for Cd1···Cd3J, 3.807 Å for Cd1···Cd4K, and 3.857 Å for Cd3···Cd4O (Symmetry codes: O: –1/2+x, 3/2+y, z; K: –1/2+x, 1/2+y, z; J: x, –1+y, z.). And the two kinds of TCPB3– ligands coordinate with the 1D {Cd6(COO)12(μ3–OH)2(μ2–OH2)2}n SBUs to form a 3D network (Figure S3), which can be further expanded into a 3D framework (Figure 6a) with the help of Cd2 ions. As can be seen above, each {Cd6(COO)12(μ3–OH)2(μ2–OH2)2} unit (Figure S4) is surrounded by twelve different TCPB3– ligands, and two kinds of TCPB3– ligands act as bridges to link {Cd6(COO)12(μ3–OH)2(μ2–OH2)2} unit, and Cd2 ions as linkers. Thus, the whole framework of 2 can topologically be described as a 12–connected with the point symbol of {312.440.512.62} after the {Cd6(COO)12(μ3–OH)2(μ2–OH2)2} unit is regarded as the 12–connected node (Figure 6b and Figure S5). And the similar 12–connected nets of CPs have been reported previously.47–50

Figure 4. The asymmetric unit of 2 (Symmetry codes: A: 1/2+x, –1/2+y, z; B: 1–x, y, 1/2–z; C: 1/2–x, –1/2+y, 1/2–z; D: 1–x, y, 3/2–z; E: 1–x, –y, –z; F: 1–x, –1+y, 1/2–z; G: 1/2–x, 1/2+y, 1/2–z; H: x, 1+y, z; I: 1/2–x, 3/2–y, –z.).

Figure 5. The 1D {Cd6(COO)12(μ3–OH)2(μ2–OH2)2}n SBUs.



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Figure 6. (a) The 3D framework of 2. (b) The Schematic view of 12–connected 3D net with the point symbol of {312.440.512.62} for 2 (dark blue spheres: {Cd6(COO)12(μ3–OH)2(μ2–OH2)2} unit.).

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5 Figure 7. The asymmetric unit of 3 (Symmetry codes: A: 2–x, 1–y, –z; 35 B: x, –1+y, z; C: 1–x, –y, 1–z; D: 1+x, y, –1+z; E: 2–x, –y, –z; F: 3–x, –y, 1–z.). (b) The trinuclear {Mn3(COO)6} SBUs.

Structural Description of [Mn1.5(TCPB)(bib)0.5(DMF)]n (3). Structural analysis reveals that complex 3 is a trinuclear 40 10 {Mn3(COO)6} SBUs based 3D 3,8–c tfz–d net, and it crystallizes in triclinic system Pī space group, and there are one and a half of MnII cations, one TCPB3– ligand, a half of bib linkers, and one coordinated DMF molecule in the asymmetric unit (Figure 7a). Mn1 is located in a 45 15 centrosymmetric distorted {MnO6} octahedral geometry, 3– linked by six carboxyl oxygen atoms from six TCPB ligands. And Mn2 lies in the centre of a distorted {MnO5N} octahedral coordination geometry, surrounded by four carboxyl oxygen atoms from three different TCPB3– ligands, 50 20 one oxygen atom form DMF, and one nitrogen atom from bib linker. Besides, the bond lengths of Mn–O are in the

range of 2.188(8)–2.621(7) Å, and those of Mn–N are 2.193(8) Å, respectively. Difference from that in 1, the H3TCPB ligand adopts (κ1–κ1)–(κ1–κ2)–(κ1–κ1)–μ7 coordination mode (Mode IV) in complex 3, with the dihedral angles of α, β, γ, δ, ε, and ζ being 80.68°, 50.30°, 88.11°, 84.26°, 57.89°, and 51.53°, respectively. Interestingly, the bridging μ2–η1:η1 carboxyl groups cooperate with the chelating+bridging μ3–η1:η2:η1 carboxyl groups to link with the MnII cations, succssfully constructing a trinuclear {Mn3(COO)6} SBUs (Figure 7b), in which the Mn1···Mn2 distances are 3.645 Å, and Mn2···Mn2E distances are 7.290 Å, respectively. Each μ7–TCPB3– linker connects with three {Mn3(COO)6} SBUs to obtain a 2D [Mn3(TCPB)2]n motif along a axis successfully (Figure 8a). And the bib ligands bridge the 2D [Mn3(TCPB)2]n motifs to form a 3D network with an interesting 1D quadrilateral channels (13.468 Å × 14.300 Å) (Figure 8b). And the large channels make those nets possible interpenetrate with each other, finally leaving a 2–fold 3D framework (Figure 8c). Topological analysis reveals that the single net can be considered as a 2–nodal 3,8–c net with stoichiometry (3–c)2(8–c) by denoting the trinuclear {Mn3(COO)6} SBUs to 8–c nodes, the TCPB3– ligands to 3–c nodes, respectively. And the topological type of 3 is tfz–d; UO3 (topos&RCSR.ttd), with the point symbol being {43}2{46.618.84} (Figure 9a and Figure S6).51 Besides, the two interpenetrating net of the final structure is shown in Figure 9b, with the FIV (Full interpenetration vectors): [1,0,0] (10.92A), and PIC: [2,0,0][0,1,0][1,0,–1] (PICVR=2); Zt=2, Zn=1; Class Ia, Z=2.

Figure 8. (a) The 2D [Mn3(TCPB)2]n motif view. (b) The single 3D net for 3 with 1D quadrilateral channels. (c) Schematic view of the 2–fold 3D frameworks of 3 along b axis.


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Figure 9. (a) The 3D (3,8)–connected {43}2{46.618.84}–tfz–d net for single network in 3 (dark blue spheres: trinuclear {Mn3(COO)6} SBUs, pale blue spheres: TCPB3– ligands.). (b) The 2–fold tfz–d net for the final whole frameworks of 3.

(Cd1A···Cd2 = 3.597 Å, Figure S7), which is further expanded

35 by the formates into a 1D {Cd2(COO)2(HCOO)}n chain with

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10. The asymmetric unit of 4 (Symmetry codes: A: x, 1–y, 1/2+z; B: 1/2+x, 1/2–y, 1/2+z; C: 1/2+x, 3/2–y, 1/2+z; D: 3/2–x, 3/2–y, 1–z; E: 1/2+x, 1/2+y, z; F: 1/2+x, –1/2+y, z; G: 3/2–x, 1/2–y, 1–z.).

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Structural Description of {[Cd2(TCPB)(HCOO)(bib)(H2O)]·0.5Dioxane}n (4). The formates which generated by DMF in–situ reaction make the complex 4 more complicated and finally giving a 3D (3,7)–c net with 1D {Cd2(COO)2(HCOO)}n chain. Complex 4 crystallizes in monoclinic system C2/c space group. Two CdII cations, one TCPB3– ligand, one formate, one bib linker, one coordinated water molecule, and a half of free dioxane molecules are included in the asymmetric unit of 4 (Figure 10). Cd1 is surrounded by five carboxyl oxygen atoms (O3, O8E, O9E, O11F, and O12F) from three TCPB3– ligands, one O4 atom from formate, and one coordinated water molecule, and presenting a distorted {CdO7} pentagonal bipyramid geometry. Cd2 lies in the centre of a distorted {CdO4N2} octahedron coordination geometry, surrounded by three carboxyl oxygen atoms (O2A, O8B, and O11C), O5 from formate, and two nitrogen atoms (N1 and N3) from two different bib linkers. Besides, the bond lengths of Cd–O are in the range of 2.210(4)–2.470(7) Å, and those of Cd–N are 2.277(3) Å and 2.297(2) Å. In 4, the TCPB3– adopts (κ1–κ1)–(κ1–κ2)–(κ1–κ2)–μ8 coordination mode (Mode V), with the dihedral angles of α, β, γ, δ, ε, and ζ being 78.38°, 78.05°, 84.40°, 84.56°, 73.44°, and 11.77°, respectively. The bridging μ2–η1:η1 as well as the chelating+bridging μ3–η1:η2:η1 carboxyl groups coordinate with CdII cations to form a binuclear {Cd2(COO)3} SBUs

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the binuclear {Cd2(COO)3}n SBUs distance being 8.843 Å (Figure S8). Each μ8–TCPB3– linker connects with three {Cd2(COO)3} SBUs, successfully obtaining a 2D [Cd2(TCPB)]n sheet with the opening area being 18.230 Å × 12.666 Å (Figure 11a). And the formates further expanded the 2D [Cd2(TCPB)]n sheets into a 3D [Cd2(TCPB)(HCOO)]n network with the area of the containing 1D channel being 16.564 Å × 6.453 Å (Figure 11b). It is worth noting that two adjacent 3D [Cd2(TCPB)(HCOO)]n networks interpenetrated with each other in 4 (Figure 12a). Moreover, the bib linkers bridge Cd2 ions to generate a 1D {Cd(bib)}n chain, and the separations of Cd···Cd are 14.001 Å, and 14.243 Å (Figure S9). With the 1D {Cd(bib)}n chains as the wear lines, the two interpenetrating [Cd2(TCPB)(HCOO)]n nets hinged together into a 3D framework (Figure 11c). From the viewpoint of topology, the final whole framework of 4 can be considered as a 2–nodal 3,7–c net with stoichiometry (3–c)(7–c) with the point symbol being {4.62}{47.614} (Figure 12b), by denoting the binuclear {Cd2(COO)3} SBUs to 7–connected nodes, the TCPB3– ligands to 3–connected nodes, and the bib linkers as well as the formates to 2–connected nodes, respectively. X–ray Powder Diffraction Analyses and thermogravimetric Analyses. To check the phase purity, the samples of complexes 1–4 were characterized by the PXRD. As can be seen in Figure S10, the experimental PXRD patterns are almost similar with the simulated ones for 1–4. Thermogravimetric analyses were investigated for 1–4 (Fig. S11). For 1, the weight loss of 8.91 % is attributed to the loss of coordinated and lattice water molecules between 100 and 210 °C (calcd: 8.74 %). Then the whole structure began to collapse above 405 °C. At first, the weight loss between 130 and 210 °C is owed to the loss of free and coordinated water molecules of 7.51 % for 2(calcd: 7.34 %), and then the framework broke down at around 380 °C. For 3, the weight loss of 9.86 % is the loss of coordinated DMF molecules below 220 °C (calcd: 9.83 %). Then the organic linkers began to degrade about 350 °C. For 4, the initial weight loss of 6.7 % in temperature range of 120–265 °C belongs to the loss of a half of free dioxane molecules and a coordinated water molecule (calcd: 6.1 %). And then the framework began to collapse.



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Figure 11. (a) The 2D [Cd2(TCPB)]n sheet in 4 along c axis. (b) The 3D[Cd2(TCPB)(HCOO)]n network with 1D channels in 4. (c) The 3D framework of 4 along c axis.

5 Figure 12. (a) The simplified net of the interpenetrated 3D [Cd2(TCPB)(HCOO)]n network in 4. (b) The (3,7)–connected {4.62}{47.614} net of 4 (grass green spheres: binuclear {Cd2(COO)3} SBUs, red spheres: TCPB3– ligands.). Table 1. The detail comparisons among 1–4. Complex Coordination mode SBUs

Complex 1 Mode I {Mn3(COO)8(μ2–H2O)2}n

Complex 2 Mode II Mode III {Cd6(COO12(μ3–OH)2(μ2–OH2)2}

M–TCPB motifs Configuration of bib M···M distance (bib) 3D architecture Point symbol

3D [Mn3(TCPB)2]n net NA NA (4,8)–connected flu net {412.612.84}{46}2

3D [Cd7(TCPB)4]n net NA NA 12–connected net {312.440.512.62}

n

Complex 3 Mode IV {Mn3(COO)6}

Complex 4 Mode V {Cd2(COO)3}

2D [Mn3(TCPB)2]n sheet Trans– 13.732 Å 2–fold (3,8)–c tfz–d net {43}2{46.618.84}

2D [Cd2(TCPB)]n sheet Trans– 14.001 Å, and 14.243 Å (3,7)–connected net {4.62}{47.614}

10 Table 2. More details of the coordination modes of I–V in 1–4. Mode Details α β γ δ ε ζ

Mode I (κ0–κ2)–(κ1–κ1)–(κ1–κ1)–μ6 83.93° 49.63° 10.03° 55.15° 89.62° 50.05°

Mode II (κ1–κ1)–(κ1–κ0)–(κ1–κ2)–μ5 69.95° 49.48° 71.64° 68.67° 72.22° 32.43°

Mode III (κ1–κ2)–(κ2–κ1)–(κ1–κ1)–μ7 58.11° 71.07° 88.45° 70.35° 74.06° 35.62°

Mode IV (κ1–κ1)–(κ1–κ2)–(κ1–κ1)–μ7 80.68° 50.30° 88.11° 84.26° 57.89° 51.53°

Mode V (κ1–κ1)–(κ1–κ2)–(κ1–κ2)–μ8 78.38° 78.05° 84.40° 84.56° 73.44° 11.77°

Luminescent Properties and sensing of small organic attributed to the mixed effects of intra–ligand and molecules and Nitrobenzene Derivatives. The ligand–to–ligand charge transitions.52–60 fluorescence spectra of 2 and 4 were examined at room To explore the sensibilities of complexes 2 and 4, DMF, 15 temperature in the solid state. It can be seen from Figure S12, DMSO, ethanol, acetonitrile, n–butyl alcohol and acetone the free H3TCPB ligand displays a strong peak at 342 nm, 30 were selected for the luminescent sensing studies. 2 mg which may be assigned to π–π* transitions of the benzene samples of 2 and 4 were dispersed in 2 mL diverse solvents rings. The emission spectra of complexes 2 and 4 exhibit with ultrasonication of 30 minutes. As shown in Figure 13, strong emission peaks at 346 nm for 2 and 314 nm for 4, both 2 and 4 display the strongest luminescent intensity in 20 respectively (λex = 280 nm). The emission peak of complex 2 DMF, while exhibit the weakest in acetone, with the is in accordance with that of the free H3TCPB ligand. While 35 intensity sort being DMF > acetonitrile > n–butyl alcohol > the emission spectrum of 4 has a clear blue shift (Δ = 26 nm) DMSO > ethanol > acetone. The recognition mechanism of because of the introduction of auxiliary ligand bib. It is organic solvents may be attributed to the interactions worth noting that the emission peak of 4 is analogous to that between the different structures of the Cd–CPs and different 25 of bib (λex = 280 nm). Thus, this phenomenon can be polarities of the solvent molecules.61


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60 Figure 13. The luminescence intensities of complex 2 (a) and 4 (b) which were dispersed in different organic solvents.

The nitroaromatics (NACs) are important chemical raw 65

5 materials and extensively applicated in leather, dyes, and the

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electron–withdrawing ability, electric properties and vapor pressure of the analytes.65 So, we speculate that the reasons for different orders are attributed to the mixed result of above–mentioned factors. As shown in Figure S23 and S24, the quenching decay is very small after three cycles; the results exhibit that 2 and 4 can be recovered and reproduced by washing with DMF and filtration. Meanwhile, the PXRD patterns of samples after the quenching experiments were similar to the simulated one, indicating complexes have good recyclability and stability as chemical sensors (Figure S25, S26). The possible quenching mechanisms of nitrobenzene derivatives as following: (1) The inductive effect of the photoinduced electron transfer mechanism.66,67 The lowest unoccupied molecular orbitals (LUMOs) of electron–deficient NACs locate in somewhere between the conduction band (CB) and valence band (VB) of the CPs. The excited electrons from the CB of the CPs can be transferred to the LUMO orbitals of NACs upon excitation, resulting in quenching effect; (2) To manifest whether RET exists or not in the sensing process, the UV−vis spectra of NACs dispersed in 2 and 4 suspensions were investigated, the results present NACs have wide absorption bands from 300 to 550 nm, which overlap with the excitation and/or emission bands of complexes 2 and 4 (Figure S27), showing resonance energy transfer (RET) exists in the quenching experiment.68–72

glass industry, which will cause explosive and have the hazard. Therefore, effective and fast detection of NACs is vital to the environment and personal safety. Herein, we selected series of nitroaromatics (NACs) (p–nitrotoluene (PNT), nitrobenzene (NB), p–nitrophenol (PNP), and p–nitroaniline (PNA)) as representatives to study the recognition of 2 and 4 for NACs, systemically. The DMF solutions of PNT, NB, PNP, and PNA with different concentrations were tested and given in Figure 14, and it can be seen that the fluorescent intensities of emulsions decreased with increasing concentrations of the DMF solution. When the concentrations of nitroaromatics in the suspension solution are up to 0.1 mM, the quenching rates of the Cd–CPs are listed in Table 3. The curves of the I0/I versus the concentration of NCVs are presented in Figure S13–S20 to further test the quenching efficiency (I0 and I are the fluorescent intensity without and with the addition the analyte, respectively).62,63 And the I0/I versus nitroaromatics concentration plots show a bend upwards, which may be attributed to the coexistence of static and dynamic quenching.64 The related parameters of the Stern–Volmer curves were listed in Table 3. The values of KSV are measured when the concentrations of NDVs are up to 10 μ M (Figure S21, S22). As it can be found that the orders of quenching constants for NCVs are PNP > PNA > NB > PNT (2) and 70 Figure 14. The photoluminescence intensities of 2 (a) and 4 (b) dissolved in the DMF with the addition of NACs. PNT > PNP > NB > PNA (4), respectively. Notably, this order is not fully in accordance with the trend of Table 3. Related parameters in the sensing of nitroaromatics for 2 and 4. Analyte Quenching rate Exponential equation Ksv (M−1) electron–withdrawing groups. The reasons for this phenomenon are as follows: Firstly, the structural difference NB 90.05% I0/I = 1.90e35654[NB]-1.03 9.4×104 of complexes 2 and 4. The H3TCPB ligand is partly and PNT 78.68% I0/I=1.53e24058[PNT]-0.52 5.4×104 2 completely deprotonated in 2 and 4, respectively. PNA 96.55% I0/I=2.95e47212[PNA]-2.23 2.5×105 37279[PNP] Furthermore, the auxiliary ligand (bib) and formats took PNP 97.12% I0/I=6.30e -5.55 3.7×105 28894[NB] part in the construction of 4; Secondly, the weak NB 87.54% I0/I=2.17e -1.16 9.7×104 interactions between CPs and nitro–containing analytes may PNT 97.13% I0/I=3.59e47093[PNT]-2.83 3.2×105 4 lead to the different orders; At last, other factors might be PNA 84.85% I0/I=1.72e29024[PNA]-0.72 8.0×104 23921[PNP] one of the important causes, including PNP 96.04% I0/I=10.6e -9.80 3.1×105



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60 Figure 15. Luminescence intensities of 2 and 4 in 0.01 M aqueous solutions of metal cations.

Detection of Metal Cations. The sensing abilities of 2

5 and 4 for different M(NO3)x (0.01 M, and M = Na+, Mn2+, Zn2+,

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Cd2+, Co2+, Ni2+, Hg2+, K+, Ca2+, Ba2+, Cu2+, Mg2+, Al3+, Cr3+) were studied in water at 25 ℃. As can be seen from the Figure 15, the luminescent intensity of Mn+@CPs was varied with different metal ions. The results show that Cr3+ cations 70 for 2 and 4 have better luminescent quenching effects. It was studied simultaneously that the relationship between the concentration of Cr3+ cations and the luminescent intensity of Cd–CPs suspensions. It can be seen from Figure S28 and S29, the fluorescent intensities of 2 and 75 4 present obvious quenching effect with increasing addition of Cr3+ cations, and the quenching rate is 96.90 % for 2 when the concentration of Cr3+ is up to 0.13 mM, and 97.67 % for 4 when the [Cr3+] is up to 0.1 mM. The nonlinearities of Stern–Volmer curves for Cr3+@CdCPs in aqueous system are conformed to the exponential equations of I0/I = 1.35e2065[Cr3+] – 0.25 for 2 , and I0/I = 2.10e2920[Cr3+] – 1.47 for 4, respectively. 80 And the SV plots are typically linear when the [Cr3+] is 0.015 mM, the Ksv value of 5.6×104 M–1 for 2 , and 3.8×104 M–1 for 4 ( Figure S30). To further investigate the anti–interference abilities of other metal ions to quenching selectivity of 2 and 4 for Cr3+, 85 the luminescent sensing of 2 and 4 suspensions for Cr3+ ions was investigated in the presence of other metal cations. The results indicate that there exists hardly any effect on the exploration of Cr3+ (Figure S31). Furthermore, the PXRD patterns of samples after fluorescent experiments are consistent with the simulated one, demonstrating that the structures of 2 and 4 don’t change (Figure S25, S26). 90 Meanwhile, as can be seen from Figure S32 that the fluorescent intensities of complexes did not show significant change, this result shows 2 and 4 have good regenerative abilities after three cycles. Therefore, 2 and 4 can sense the Cr3+ cations in aqueous solution. Based on the 95 above–mentioned results, the possible quenching mechanisms of 2 and 4 for NACs analytes might be as follows: (1) the competition absorption for the excitation energy between the Cr3+ and CPs frameworks due to their weak interactions or the bonding interactions;73–75 (2) Researchers have found that the overlap of absorption by the 100 analytes with the excitation and/or emission of the complexes might cause the intermolecular energy transfer.76-77 In order to verify the absence or presence of the intermolecular energy transfer in our system, the UV–vis

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spectra of Cr3+ in aqueous solution of 2 and 4 were carried out, the results show that Cr3+ has wide absorption bands from 300 to 650 nm, which overlap with the excitation and/or emission bands of complexes 2 and 4 (Figure S33). Magnetic Properties. The crystal structures reveal that 1D rod–like {Mn3(COO)8(μ2–H2O)2}n SBUs in 1, and trinuclear {Mn3(COO)6}n SBUs in 3 may show magnetic properties. Thus, the variable–temperature magnetic susceptibility measurements of 1 and 3 are shown in Figure S34 and S35. For complex 1, the χMT value at room temperature is 14.3 cm3 K mol–1, and similar with three spin–only magnetically isolated MnII ions (13.2 cm3 K mol–1), which may be due to the antiferromagnetic interactions between MnII ions.78With the temperature decreasing to 14.5 K, the χMT value decreases to the lowest of 7.6 cm3 K mol–1. And then the χMT value up to 13.5 cm3 K mol–1 at about 2K. The temperature dependence χM followed the Curie–Weiss law χM = C/(T–θ) with C = 15.5 cm3 K mol–1, θ= –28.6 K (Figure S34). For complex 3, the variable–temperature susceptibility is similar to 1, with the χMT value being 13.6 cm3 K mol–1 at room temperature, according with the superposition of three spin–only magnetically isolated MnII ions (13.2 cm3 K mol–1).79 And then the χMT value decreases continuously to 4.3 cm3 K mol–1 with the temperature decreasing to 2K. The temperature dependence χM also followed the Curie–Weiss law χM = C/(T–θ), with C = 14.9 cm3 K mol–1, θ = –28.8 K (Figure S35). The negative values of θ also indicate that 1 and 3 have the antiferromagnetic exchange interactions between the adjacent MnII ions. CONCLUSION In summary, four 3D CPs with diverse SBUs have been constructed, with their structures ranged from 3D (4,8)–connected flu net (1), 3D 12–connected {3 12 .4 40 .5 12 .6 2 } net (2), 2–fold interpenetrated 3D (3,8)–connected tfz–d net (3), to 3D (3,7)–connected {4.6 2}{4 7.6 14 } net (4). The magnetic investigation indicated complexes 1 and 3 have the antiferromagnetic exchange interactions between the adjacent Mn II ions. And the fluorescence measurements show 2 and 4 exhibit highly sensitive and selective detection for Cr3+ cations and nitrobenzene derivatives.

ASSOCIATED CONTENT Supporting Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxxx. Tables of crystallographic data and structure refinement details, the selected bond lengths and angles, additional crystal structure figures, powder X–ray diffraction patterns, TGA curves, emission spectra, quenching efficiency plots, and the X–ray crystallographic data in CIF format.

AUTHOR INFORMATION Corresponding Author *[email protected] “Tuoping Hu” *[email protected] “Liming Fan” ORCID Tuoping Hu: 0000-0001-7437-3246


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Liming Fan: 0000-0003-4615-0533 Notes The authors declare no competing financial interest.

65

ACKNOWLEDGEMENT

5 This work was supported by financial support from the

National Natural Science Foundation of China (No. 21601163, 70 and No. 21676258), the Foundation of State Key Laboratory of Coal Conversion (No:J17–18–611), and International Science & Technology Cooperation Program of China (No: 10 2011DFA51980). 75

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Table of Contents Graphic and Synopsis 5 Structural

Diversity, Magnetic Properties, Luminescent Sensing of Flexible Tripodal Ligand of 1,3,5–Tris(4–carbonylphenyloxy)benzene Based Mn(II)/Cd(II) Coordination Polymers Jie Zhang, Liangqin Huo, Xiaoqing Wang, Kegong Fang, Liming Fan,* and Tuoping Hu* Based on the flexible tripodal ligand of 1,3,5–tris(4–carbonylphenyloxy)benzene, four 3D Mn(II)/Cd(II) CPs have been obtained

10 with the structure ranged from 3D (4,8)–connected flu net, 3D 12–connected {312.440.512.62} net, 2–fold interpenetrated 3D

(3,8)–connected tfz–d net, to 3D (3,7)–connected {4.62}{47.614} net. The magnetic measurements indicate that 1 and 3 have the antiferromagnetic exchange interactions between the adjacent MnII ions of the SBUs. And the fluorescence measurements show 2 and 4 exhibit highly sensitive and selective detection for Cr3+ cation and nitrobenzene derivatives (nitrobenzene, p–nitrotoluene, p–nitroaniline, and p–nitrophenol).

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Structural Diversity, Magnetic Properties, and Luminescent Sensing of

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