Hydrolysis Controlled Synthetic Strategy and Structural Variation of

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Hydrolysis Controlled Synthetic Strategy and Structural Variation of Hydroxyl-Metal Clusters and Metal-Organic Frameworks Based on Tripodal Ether-Linked 1,3,5-Tris(carboxymethoxy)benzene Jia-Yao Zhang, Xue-Li Ma, Zhao-Xi Wang, Xiang He, Min Shao, and Ming-Xing Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00010 • Publication Date (Web): 22 Feb 2019 Downloaded from http://pubs.acs.org on February 23, 2019

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Crystal Growth & Design

Hydrolysis Controlled Synthetic Strategy and Structural Variation of Hydroxyl-Metal Clusters and Metal-Organic Frameworks Based on Tripodal Ether-Linked 1,3,5-Tris(carboxymethoxy)benzene Jia-Yao Zhang,† Xue-Li Ma,† Zhao-Xi Wang,† Xiang He,† Min Shao,‡ and Ming-Xing Li*,† † Department ‡ Laboratory

of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China.

for Microstructures, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China.

RECEIVED DATE

ABSTRACT: Eight novel coordination polymers were prepared by a tripodal ether-linked tricarboxylic acid: [Mn3(TCMB)2(H2O)4]n·4nH2O (1), [Cu3(TCMB)(μ3-OH)3]n·0.5nH2O (2), [Zn3.5(TCMB)2(μ2-OH)(H2O)4]n·2nH2O (3), [Zn2(TCMB)(4-abpt)(μ3-OH)]n·nH2O (4), [Cd2(TCMB)(pdta)(EtOH)(H2O)]n·2nH2O (5), [Co3(TCMB)2(bpee)3(MeOH) (H2O)5]n (6), and [Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O (7, 8) (H3TCMB = 1,3,5-tris(carboxymethoxy)benzene, 4-abpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, Hpdta = 4-(1H-tetrazol-5-yl)pyridine, bpee = 1,2-bis(4-pyridyl)ethene). These complexes were characterized by EA, IR, TGA, PXRD and single crystal XRD. H3TCMB is fully deprotonated, and flexible TCMB3– ligand exhibits nine coordination modes and various conformations. Complex 1 is a 2D coordination polymer constructing from [Mn(μ2-COO)2]n linear chain and [Mn2(μ2-COO)2(μ3-COO)2]n double-chain combined by hexadentate TCMB3– spacer. Complex 2 is a beautiful 2D sandwich-like network assembled by layered [Cu3(μ3-OH)3]n network and typical tripodal hexadentate TCMB3− ligand. Complex 3 is a 3D coordination polymer constructing from two distinct heptadentate TCMB3– ligands, in which the ether oxygen atoms take part in coordination. Complex 4 exhibits a 2D double-layered network built by tetranuclear zinc cluster [Zn4(μ2-COO)4(μ3-OH)2] pillared by pentadentate TCMB3– spacer and 4-abpt linker. Complex 5 displays a 3D architecture assembled by tridentate pdta– and heptadentate TCMB3– ligand with ether-oxygen coordination. Cobalt complexes 6–8 were prepared by similar reactions at slightly different temperature (85, 100 and 120 °C). Complex 6 is a 3D coordination polymer assembled by tridentate TCMB3– ligand. Complex 7 is a 3D porous MOF possessing tetranuclear cobalt cluster [Co4(μ2-COO)3(μ3-COO)2(μ3-OH)2] combined by hexadentate and tetradentate TCMB3– ligands. Complex 8 is a cluster-based 3D porous MOF, which is an isomer of 7 and contains different tetranuclear cluster [Co4(μ2-COO)6(μ3-OH)2] and pentadentate TCMB3– ligand. PXRD study reveals the hydrolysis reaction mechanism. A hydrolysis controlled synthesis strategy is suggested based on Ksp values of metal hydroxides. Their thermal stabilities were investigated. Complexes 1, 2, 7 and 8 present antiferromagnetic and/or ferromagnetic interactions. Their magneto-structural correlations are studied. Keywords: Coordination polymer; 1,3,5-Tris(carboxymethoxy)benzene; Crystal structure; Hydrolysis; Magnetism. purposeful design and controllable synthesis of CPs and INTRODUCTION Since 1990s, coordination

polymers

(CPs)

and

metal-organic frameworks (MOFs) have attracted much attention,1–5 not only for their intriguing architectural and topological varieties,6,7 but also for their multifunctional physical and chemical properties such as magnetism, luminescence, gas storage, catalysis, ferroelectricity and sensor.8–13 Although much effort has been paid on the

MOFs, it is still a great challenge to synthesize these functional complexes with interesting network structures and properties. To harvest novel CPs and MOFs, it depends on a variety of reaction parameters including metal ion, ligand, pH value, solvent, temperature, reagent ratio, additive, etc.14–18 There is no doubt that the structural attribution of an organic multidentate ligand plays a crucial

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Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

role in controlling the complex structure as well as topology of the derived

framework.19–21

Page 2 of 21

the ligand to metal centers. Three ether oxygen atoms may

Moreover, similar

function as electron-donors forming hydrogen bonds to

reactants often result in completely different structures due

stabilize the network structure, even coordinate to metal

to the extreme sensitivity of self-assembly to the reaction

ions. Therefore H3TCMB is a potential valuable flexible

conditions. To date, the abundant examples of temperature-

tripodal ligand.

and solvent-dependent structural variation of coordination

Although H3TCMB was synthesized in 2002,40,41 its

polymers have been doccumented.22–24 In most cases,

coordination feature has rarely been investigated yet. Only

different structures lead to different functional properties.

four papers containing nine H3TCMB complexes were

Particularly, many coordination polymers have interesting

documented.41–44 In this work, we used five metal acetates

magnetic properties.25–27 The study related to their

reacted with H3TCMB and three N-heterocyclic auxiliary

magnetism and structures is very active. Paramagnetic

ligands in neutral aqueous solutions, successfully prepared

metal ions can form clusters, chains or sheets which can be

eight novel CPs and MOFs. These complexes exhibit

linked by bridging groups such as carboxylic, hydroxyl and

interesting 2D and 3D networks originating from the

N-heterocyclic groups to produce various coordination

versatile coordination modes and conformations of

Towards

H3TCMB. Hydrolysis reactions at different temperatures

these goals, a number of polycarboxylic acids have been

play important roles in constructing their hydroxyl-

employed to prepare magnetic coordination polymers,

containing metal clusters. By comparing the precipitation-

owing to the fact that carboxylic group has diverse binding

dissolution equilibrium constant Ksp values of MII(OH)2 (M

ability that can efficiently transmit magnetic interaction.30

= Mn, Co, Cu, Zn, Cd), we discuss their hydrolysis

polymers with varied magnetic

properties.28,29

Generally, rigid aromatic polycarboxylates can lead to predictable network structures and produce highly stable

procedures in detail. Scheme 1. H3TCMB and N-Heterocyclic Ligands

coordination polymers, which have been extensively

COOH

investigated to construct coordination polymers. By

O

contrast, flexible and semirigid polycarboxylates can adopt varied conformations and coordination modes suitable for metal geometric requirement and sensitive reaction

N HOOC

O

O

COOH

H3TCMB

H N N N N

Hpdta

conditions, which may afford unpredictable coordination polymers and uncommon frameworks.31–33 Recently, ether-linked

polycarboxylates

have

attracted

intense

attention in constructing coordination polymers, Because

N

NH2 N N N

N

N N

4-abpt

bpee

the freely rotating ether bond can bring conformational change and structural flexibility.34–36 In order to extend our research in ether-linked tetracarboxylate

EXPERIMENTAL SECTION

we

Materials and Methods. H3TCMB and N-heterocyclic

acid,

ligands were purchased from Jinan Henghua Sci. & Tec.

1,3,5-tris(carboxymethoxy)benzene (H3TCMB, Scheme 1),

Co. Ltd. (China). Elemental analyses (C, H, and N) were

for our study. In comparison with the intensively

carried out with a Vario EL-III analyzer. Infrared spectra

investigated rigid 1,3,5-benzenetricarboxylic acid, the

(KBr pellet) were recorded by a Nicolet A370 FT-IR

flexible H3TCMB has good ligating ability to metal ions

spectrometer in 400–4000 cm–1. Thermal analyses were

and exhibits additional interesting characteristics, such as

performed by a Netzsch STA 449C thermal analyzer at a

the freely rotating ether bonds and flexible tripodal

heating rate of 10°C min–1 in air. Powder X-ray diffractions

conformation. Three –O–CH2– groups can bend to enable

(PXRD) were completed on a Rigaku D/MAX-2550

chose

a

tripodal

ether-linked

complexes,37–39

tricarboxylic


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diffractometer at a scanning rate of 5° min–1 in 5–50° (2θ).

[Cd2(TCMB)(pdta)(EtOH)(H2O)]n·2nH2O

(5).

A

Magnetic susceptibilities as a function of temperature in the

mixture of Cd(OAc)2·2H2O (0.20 mmol), H3TCMB (0.05

range of 2–300 K were measured on a Quantum Design

mmol), Hpdta (0.10 mmol), ethanol (4 mL) and water (4

MPMS-XL7 SQUID magnetometer at the magnetic field of

mL) was sealed in a Teflon-lined reactor (15 mL) and

1 kOe. Diamagnetic corrections were applied by using

heated at 85 °C for 72 h. Light yellow sheet crystals were

Pascal’s constants.

harvested in 54% yield. Anal. Calcd for C20H25N5O13Cd2: C,

Syntheses of Complexes 1–8.

31.27; H, 3.28; N, 9.11. Found: C, 30.42; H, 3.13; N, 9.35.

[Mn3(TCMB)2(H2O)4]n·4nH2O (1). A mixture of

IR: 3471m, 3090w, 2989w, 1579s, 1430s, 1326m, 1165s,

Mn(OAc)2·4H2O (0.20 mmol), H3TCMB (0.05 mmol),

1072m, 845m, 718s, 643m cm–1.

4-abpt (0.05 mmol), ethanol (4 mL) and water (4 mL) was

[Co3(TCMB)2(bpee)3(MeOH)(H2O)5]n (6). A mixture

sealed in a Teflon-lined reactor (15 mL) and heated at 100

of Co(OAc)2·4H2O (0.30 mmol), H3TCMB (0.05 mmol),

°C for 72 h. Light yellow sheet crystals were harvested in

bpee (0.10 mmol), methanol (4 mL) and water (4 mL) was

30%

for


C24H34O26Mn3: C, 31.91; H, 3.79. Found: C, 33.22; H, 3.85.

°C for 72 h. Pink sheet crystals were harvested in 44%

IR: 3389m, 2967w, 1615s, 1415s, 1334m, 1267m, 1170s,

yield. Anal. Calcd for C61H62N6O24Co3: C, 50.88; H, 4.34;

1079m, 821m, 726s, 629m cm–1.

N, 5.83. Found: C, 49.29; H, 4.52; N, 5.07. IR: 3190w,

yield

based

on

H3TCMB.

Anal.

Calcd

[Cu3(TCMB)(μ3-OH)3]n·0.5nH2O (2). A mixture of Cu(OAc)2·2H2O (0.20 mmol), H3TCMB (0.05 mmol),

3064w, 2909w, 1607s, 1417s, 1322m, 1260m, 1165s, 1077m, 832s, 715m, 554m cm–1.


[Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O (7). A


mixture of Co(OAc)2·4H2O (0.30 mmol), H3TCMB (0.05

°C for 72 h. Blue sheet crystals were harvested in 44%

mmol), bpee (0.10 mmol), methanol (4 mL) and water (4

yield. Anal. Calcd for C12H13O12.5Cu3: C, 26.31; H, 2.39.


Found: C, 27.11; H, 2.81. IR: 3543s, 2932w, 1594s, 1430s,

heated at 100 °C for 72 h. Pink rod crystals were harvested

1260m, 1155s, 1074m, 937s, 812m, 724s, 507s

cm–1.

in 43% yield. Anal. Calcd for C48H68N4O34Co4: C, 38.93; H,

[Zn3.5(TCMB)2(μ2-OH)(H2O)4]n·2nH2O (3). A mixture

4.63; N, 3.78. Found: C, 40.45; H, 4.61; N, 3.98. IR:

of Zn(OAc)2·2H2O (0.20 mmol), H3TCMB (0.05 mmol),

3557w, 3380m, 3079w, 2936w, 1607s, 1416s, 1334s,


1154s, 1070s, 837s, 679m, 554m cm–1.


[Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·5nH2O (8). A

°C for 72 h. Colorless sheet crystals were harvested in 24%

mixture of Co(OAc)2·4H2O (0.30 mmol), H3TCMB (0.05

yield. Anal. Calcd for C24H31O25Zn3.5: C, 30.40; H, 3.30.

mmol), bpee (0.10 mmol), methanol (4 mL) and water (4

Found: C, 31.15; H, 3.51. IR: 3444m, 3094w, 2934w,


1598s, 1410s, 1302m, 1162s, 1082m, 838m, 731m cm–1.

heated at 120 °C for 72 h. Pink block crystals were

[Zn2(TCMB)(4-abpt)(μ3-OH)]n·nH2O (4). A mixture of

harvested in 36% yield. Anal. Calcd for C48H68N4O34Co4: C,

Zn(OAc)2·2H2O (0.20 mmol), H3TCMB (0.05 mmol),

38.93; H, 4.63; N, 3.78. Found: C, 40.11; H, 4.49; N, 3.87.


IR: 3596w, 3072w, 2931w, 1597s, 1421s, 1336m, 1163s,


1081m, 832m, 720m, 550m cm–1.

°C for 72 h. Light yellow sheet crystals were harvested in

X-ray Crystallography. Single crystals of 1–8 were

49% yield. Anal. Calcd for C24H22N6O11Zn2: C, 41.11; H,

selected for X-ray diffraction study. The crystal data were

3.16; N, 11.98. Found: C, 40.95; H, 3.07; N, 11.77. IR:

collected on a Bruker Smart Apex-II CCD diffractometer

3319m, 3095w, 2966w, 1608s, 1407s, 1292m, 1157s,

with graphite-monochromatic Mo-Kα radiation (λ =

1071m, 836s, 714s, 601m cm–1.

0.71073 Å) at 296 K. The determinations of crystal system, ACS Paragon Plus Environment


Page 4 of 21

orientation matrix, and cell dimensions were performed

Mn2···Mn2B distance of 4.645(2) Å. The 1D linear chain

according to established procedures. Their structures were

and double-chain are further connected by the aromatic

solved by direct methods.45 Non-hydrogen atoms were

ring of TCMB3− to form the final 2D network of complex 1,

refined anisotropically. Hydrogen atoms were placed

as depicted in Figure 1c. Previously, a binuclear complex

geometrically and refined using the riding model.

(H2bipy)[Mn2(HTCMB)2(H2O)8]·5H2O

Crystallographic data have been deposited with the

from bidentate HTCMB2– ligand.41

was

constructed

Cambridge Crystallographic Data Center with the CCDC numbers 1888154−1888161. Their key crystallographic data are summarized in Table 1. Selected bond distances

(a)

and angles are listed in Table S1 (Supporting Information). Hydrogen bonds are collected in Table S2. RESULTS AND DISCUSSION Crystal Structural Description. [Mn3(TCMB)2(H2O)4]n·4nH2O (1). Complex 1 is a 2D coordination polymer. The asymmetric unit contains one and a half crystallographically independent Mn(II) ions, a

(b)

TCMB3– ligand, two coordinated water molecules and two lattice water molecules (Figure 1a). Mn1 (0.5 occupancy) locates at the center of a symmetric octahedral geometry, coordinated by four carboxylic oxygens and two water molecules (O11, O11A). The Mn1−O9, Mn1−O10 and Mn1−O11 bond distances are 2.246(2), 2.137(2) and 2.187(2) Å, respectively. Mn2 adopts a distorted octahedral geometry, coordinated by five carboxylic oxygens and water O4 atom. Mn2−O4 bond distance is 2.199(4) Å. The carboxylic Mn2–O bond distances vary from 2.139(2) to

(c)

2.260(3) Å. Three carboxylic groups of H3TCMB are fully deprotonated. TCMB3− anion acts as a hexadentate ligand and adopts coordination mode I (Scheme 2), which possesses two bidentate syn-syn η1η1-μ2-carboxylic groups and a bidentate-bridging η1η2-μ3-carboxylic group. One η1η1-μ2-carboxylic group links Mn1 (0.5 occupancy) and Mn1A to form a 1D [Mn(μ2-COO)2]n linear chain (Figure 1b). Mn1···Mn1A distance is 4.645(2) Å. Another η1η1-μ2-carboxylic group and the η1η2-μ3-carboxylic group link Mn2 ions to form a 1D [Mn2(μ2-COO)2(μ3-COO)2]n double-chain. The η1η2-μ3-carboxylic group links Mn2 and Mn2A via O5 bridging atom with a Mn2···Mn2A distance of 3.537(1) Å, and binds to Mn2B via O3B terminal with a

Figure 1. (a) Coordination structure of 1, lattice water and hydrogen atoms are omitted for clarity. (b) 1D [Mn(μ2-COO)2]n chain (up), and 1D double-chain [Mn2(μ2-COO)2(μ3-COO)2]n (down). (c) 2D network. [Cu3(TCMB)(μ3-OH)3]n·0.5nH2O (2). Complex 2 is a 2D sandwich-like coordination polymer, which crystallizes in trigonal P-3 space group and has a C3 symmetric axis. The asymmetric unit contains an independent Cu(II) ion, 1/3 TCMB3– ligand, a μ3-OH– ligand, and 1/6 lattice water molecule. Cu1 adopts a square-pyramidal geometry (Figure 2a), coordinated by two carboxylic oxygens (O1A, O3) and


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three hydroxyl oxygens (O2, O2A, O2B). Hydroxyl O2A

Complex 2 is the first example to exhibit perfect

atom occupies the apical position with a Cu1–O2A bond

tripodal coordination conformation of TCMB3− ligand. Due

distance of 2.266(5) Å. Other two hydroxyl Cu1–O2 and

to the flexibility of ether linkage, TCMB3− presents a

Cu1–O2B bond distances are 1.926(4) and 1.945(4) Å,

typical tripodal conformation with almost perpendicular

while O1A–Cu1–O3 and O2–Cu1–O2B bond angles are

dihedral angle (86.73º) between three carbethoxyl groups

159.7(2) and 175.8(1)°, respectively.

and central phenyl ring. TCMB3− is a hexadentate ligand, which

(a)

η1η1-μ

has

three

2-carboxylic

identical

bidentate

syn-syn

groups (mode II, Scheme 2). Each

TCMB3− captures six Cu(II) ions to afford a sandwich-like 2D [Cu3(TCMB)]n network (Figure 2b). The inner copper ions are further connected by μ3-hydroxyl groups to form a layered

[Cu3(μ3-OH)3]n

network

that

possesses

honeycomb-like 12-membered ring with the pore diameter of 6.479(2) Å (Figure 2c). The [Cu3(μ3-OH)3]n layer is sandwiched between two organic layers originating from (b)

the tripodal TCMB3− ligands. This combination produces a 2D porous sandwich-like network with the thickness of about 8.4 Å (Figure 2d). The identical 2D networks are parallel packed along the c-axis, as depicted in Figure S1 (Supporting Information). [Zn3.5(TCMB)2(μ2-OH)(H2O)4]n·2nH2O (3). Complex 3 is a 3D coordination polymer. The asymmetric unit

(c)

contains three and a half independent Zn(II) ions, two TCMB3– ligands, a μ2-OH– ligand, four H2O ligands and two lattice H2O molecules (Figure 3a). Zn1 adopts a tetrahedral geometry, coordinated by carboxylic O9 and O10 atoms, hydroxyl O8 atom, and water O11W atom. Zn2 adopts a distorted octahedral geometry, coordinated by two monodentate carboxylic groups (O5, O7), water O6W, hydroxyl O8, and two ether oxygen atoms (O3, O12). Zn2–O3 and Zn2–O12 bond distances are 2.528(4) and

(d)

2.487(6) Å, respectively. Previously, the phenomenon of ether oxygen coordination was observed in a Cu-TCMB complex, in which the Cu–O bond distance is 2.412(2) Å.42 Zn3 locates at the center of an octahedral geometry, coordinated by four carboxylic oxygens (O15, O16, O17, O19) on equatorial plane. Ether O14 and water O18W atoms occupy the axial positions with the O14–Zn3–O18W

Figure 2. (a) Coordination structure of 2. (b) Sandwichlike [Cu3(TCMB)]n network. (c) [Cu3(μ3-OH)3]n layer. (d) 2D porous sandwich-like network viewed along the c- and b-axes.

bond angle of 149.8(1)º and the Zn3–O14 distance of 2.402(3) Å. Zn4 (0.5 occupancy) is weakly coordinated by three carboxylic oxygens and two water molecules (O21W,



Page 6 of 21

O6a). Five Zn4–O distances are in the 2.662(4)–2.859(4) Å

μ2-hydroxyl group connect Zn1, Zn2 and Zn3 to afford a

range, longer than normal coordination bond. Therefore,

complicate 3D coordination polymer (Figure 3b). Zn4 (0.5

Zn4 can be deemed as a charge counterion.

occupancy) has weak combination with five O-donors and balances the charge from μ2-OH– anion.

(a)

[Zn2(TCMB)(4-abpt)(μ3-OH)]n·nH2O (4). Complex 4 is a 2D double-layered coordination polymer. The asymmetric unit contains two independent Zn(II) ions, a TCMB3−, a 4-abpt, a μ3-OH− ligand and a lattice water molecule. Zn1 is surrounded by three carboxylic oxygens, pyridyl N1 and two hydroxyl oxygens (O3, O3A), completed an octahedral geometry (Figure 4a). Zn2 adopts a tetrahedral geometry, coordinated by two carboxylic oxygens, pyridyl N2 and hydroxyl O3 atoms. All the Zn−O bond distances vary from 1.944(3) to 2.216(3) Å, except a slightly longer Zn1−O4 bond (2.415(4) Å). Average Zn–N distance is 2.039(4) Å.

(b)

(a)

Figure 3. (a) Coordination structure of 3. (b) 3D framework. Two TCMB3– ligands adopt heptadentate coordination modes III and IV (Scheme 2). In mode III, a bidentate bridging carboxylic group (O17, O10c) to link Zn3 and

(b)

Zn1c. Ether O14 atom binds to Zn3 to form a five-membered chelating ring. Similarly, another bidentate bridging carboxylic group (O7, O24) links Zn2 and Zn4c, and ther O12 atom coordinates to Zn2, forming a five-membered chelating ring. A monodentate carboxylic group binds to Zn1 by O9 atom. In mode IV, a bidentate bridging carboxylic group (O19, O20) links Zn3 and Zn4. A carboxylic group (O15, O16) chelates to Zn3, while ether

(c)

O1 atom coordinated weakly to Zn4. A monodentate carboxylic group (O4, O5) coordinates to Zn2 via O5 atom, together with ether O3 atom binding to Zn2, forming a five-membered chelating ring. Moreover, the μ2-OH– ligand (O8) links Zn1 and Zn2 with a Zn1···Zn2 distance of

Figure 4. (a) Coordination structure of 4. (b) 1D [Zn2(TCMB)(μ3-OH)]n ribbon (up), and 2D doublelayered network (down). (c) Parallel packing diagram.

3.5002(8) Å. Finally, two distinct TCMB3– ligands and the ACS Paragon Plus Environment

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Crystal Growth & Design TCMB3− is pentadentate and adopts coordination mode

and 86.0° with the central phenyl ring. Each TCMB3−

V (Scheme 2), which possesses a monodentate carboxylic

combines five Cd(II) ions to afford a wave-like 2D

group and two bidentate bridging η1η1-μ2-carboxylic groups.

double-layered [Cd2(TCMB)]n network (Figure 5b). The

Every TCMB3− ligand combines five zinc ions. Three

pdta− anion is a planar tridentate ligand, which links Cd1

carbethoxyl groups twist 59.8°, 62.7° and 63.7° with the

and Cd2 via the tetrazolyl group to form a Cd2 dimer with a

central phenyl ring. The μ3-hydroxyl group connects three

Cd1···Cd2 distance of 3.987(1) Å (Figure 5b). Its pyridyl

zinc ions, and the Zn1−O3, Zn1A−O3 and Zn2−O3 bond

group further links Cd2 ion in adjacent [Cd2(TCMB)]n

distances

Å,

network. Therefore, the 2D double-layered [Cd2(TCMB)]n

respectively. A pair of Zn1/Zn1A and a pair of Zn2/Zn2A

networks are parallel arranged and further linked by pdta−

are connected by two μ3-hydroxyl groups and four

to construct a 3D coordination polymer (Figure 5c).

are

2.023(3),

2.216(3)

and

1.944(3)

bidentate bridging carboxylic groups to form a tetranuclear [Zn4(μ2-COO)4(μ3-OH)2]

cluster

with

a

Zn1···Zn1A

distance of 3.14(2) Å. The tetranuclear cluster as a secondary building unit (SBU) is further linked by

(a)

TCMB3−

spacer to afford a 1D [Zn2(TCMB)(μ3-OH)]n ribbon. These identical ribbons are parallel arranged and pillared by bidentate 4-abpt linker to generate a 2D double-layered coordination polymer (Figure 4b). The double-layered networks are parallel packed, as depicted in Figure 4c. [Cd2(TCMB)(pdta)(EtOH)(H2O)]n·2nH2O

(5).

Complex 5 is a 3D coordination polymer. The asymmetric

(b)

unit contains two independent Cd(II) ions, a TCMB3− and a pdta− ligands, an ethanol and a water ligands, and two lattice water molecules. Cd1 is octahedrally coordinated by three carboxylic oxygens, ethanol O9, water O7 and tetrazolyl N3 atoms (Figure 5a). Cd2 adopts a pentagonbipyramidal

geometry,

seven-coordinated

by

four

carboxylic oxygens, ether O4, pyridyl N5 and tetrazolyl N1 atoms. The apical positions are occupied by N5 and O5

(c)

atoms with a N5–Cd2–O5 bond angle of 173.6(1)°. Cd–O bond distances vary from 2.191(3) to 2.460(2) Å, except a weak ether oxygen coordination bond (Cd2–O4: 2.715(3) Å). Three Cd–N distances are in the 2.284(3)–2.337(3) Å

Figure 5. (a) Coordination structure of 5. (b) Wave-like 2D [Cd2(TCMB)]n network (up), and Cd-pdta zigzag chain (down). (c) 3D framework of 5.

range. TCMB3− is heptadentate and adopts coordination mode VI (Scheme 2). A carboxylic group chelates to Cd2A. A chelating-bridging η1η2-μ2-carboxylic group chelates to Cd1 and bridges Cd2 via O5 atom. A bidentate bridging η1η1-μ2-carboxylic group links Cd1B and Cd2B, while ether O4A atom binds to Cd2B, forming a five-membered chelating ring. Three carbethoxyl groups twist 52.0°, 61.1°

[Co3(TCMB)2(bpee)3(MeOH)(H2O)5]n (6). Complex 6 is a 3D coordination polymer. The asymmetric unit contains three independent Co(II) ions, two TCMB3– ligands, three bpee ligands, a methanol ligand and five coordinated water molecules. As shown in Figure 6a, Co1 adopts a cis-octahedral geometry completed by two carboxylic oxygens, two pyridyl nitrogens, and two water



Page 8 of 21

oxygens (O1, O2). N1–Co1–N2 bond angle is 91.1(1)º.

(Figure 6b). Three distinct bpee ligands are bidentate and

Similarly, Co2 adopts a cis-octahedral geometry completed

connect Co(II) ions via their pyridyl terminals to form a 1D

by two carboxylic oxygens, two pyridyl nitrogens, and two

[Co3(bpee)3]n zigzag chain. The cross-linking of the 1D

water oxygens (O10, O11) with a N3–Co2–N4 bond angle

[Co3(bpee)3]n chain and 1D [Co3(TCMB)2]n ribbon

of 92.2(1)º. Co3 locates at the center of a trans-octahedral

facilitates the extension of 6 to a 3D framework, in which

geometry, coordinated by two carboxylic oxygens, two

the coordinated methanol and water molecules bind to

pyridyl nitrogens, water O21 and methanol O22 atoms.

Co(II) ions (Figure 6c). Previously, a 1D ladder-like

N5–Co3–N6 bond angle is 179.1(2)º. All the Co–O bond

{[Cd2(HTCMB)2(bpee)(H2O)4]·bpee·2H2O}n complex was

distances vary from 2.056(4) to 2.214(2) Å. Co–N

constructed, which was extended to a 2D supramolecular

distances are in the 2.083(3)–2.198(4) Å range.

network via bpee guest connector.44 [Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O

(7).

Complex 7 is a 3D porous coordination polymer. The

(a)

asymmetric unit consists of four independent Co(II) ions, two TCMB3– ligands, two bpee ligands, two μ3-OH− ligands, two coordinated water and twelve lattice water molecules. As shown in Figure 7a, all the Co(II) ions adopt distorted octahedral geometry, coordinated by a nitrogen atom and five oxygen atoms. Taking Co1 for instance, the equatorial plane is completed by two μ3-hydroxyl oxygens (O7, O9), carboxylic O1 and pyridyl N1 atoms. N1–Co1–O7 and O1–Co1–O9 bond angles are 175.2(1)º

(b)

and 177.5(1)º, respectively. The axial positions are occupied by carboxylic O4 and O5 atoms with a O4–Co1–O5 bond angle of 172.2(1)º. Co2 is coordinated by three carboxylic oxygens (O8, O10, O13), hydroxyl O9, pyridyl N2 and water O12W atoms. Co3 is similar to Co2, coordinated by hydroxyl O7 and water O15W atoms. Co4 is similar to Co1, combined with two hydroxyl groups (O7, O9). All the Co–O bond distances vary from 2.000(3) to

(c)

2.315(3) Å. Four Co–N distances vary from 2.093(4) to 2.139(4) Å. (a) Figure 6. (a) Coordination structure of 6. (b) 1D [Co3(TCMB)2]n ribbon (up), and 1D [Co3(bpee)3]n zigzag chain (down). (c) Perspective diagram of 3D framework. Two

TCMB3–

anions

are

tridentate

and

adopt

coordination mode VII (Scheme 2). Each TCMB3– ligand combines with three Co(II) ions via three monodentate carboxylic groups to form a 1D [Co3(TCMB)2]n ribbon ACS Paragon Plus Environment

Page 9 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design molecules are incorporated into the channels as guest molecules. [Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O

(b)

(8).

Complex 8 is a 3D coordination polymer. It is an isomer of 7 with obviously different unit cell dimensions and coordination structure. Complex 8 has a tetranuclear cobalt cluster [Co4(μ2-COO)6(μ3-OH)2] as SBU (Figure 8a), which is different from the [Co4(μ2-COO)3(μ3-COO)2(μ3-OH)2] in 7. Co2 is cis-octahedrally coordinated by two nitrogens and four oxygens, while Co4 is coordinated by six oxygens without nitrogen atom. However, every cobalt ion in 7 is coordinated by a nitrogen atom and five oxygen atoms. In 8,

(c)

Co1 and Co3 are both coordinated by a hydroxyl group, a pyridyl group, three carboxylic groups and a water molecule. Figure 7. (a) Coordination structure of 7, and tetranuclear cobalt cluster. (b) 2D [Co4(TCMB)2(μ3-OH)2]n network. (c) 3D framework.

All the Co–O bond distances (2.023(3)–2.229(3) Å) and Co–N bond distances (2.117(3)–2.167(3) Å) are normal as expected.

One TCMB3– is hexadentate and adopts coordination mode I. Two bidentate syn-syn η1η1-μ2-carboxylic groups

(a)

link Co1/Co3 and Co1/Co4. One η1η2-μ3-carboxylic group links Co1/Co2 by O4/O8 atoms and binds to Co3 via O4 atom. Another TCMB3– is tetradentate and adopts mode VIII (Scheme 2). One bidentate syn-syn η1η1-μ2-carboxylic group (O10, O11) links Co2/Co4. Another η1η2-μ3carboxylic group links Co3/Co4 and binds to Co2 via O13 atom. The third carboxylic group is uncoordinated. Besides, one μ3-OH− connects Co1, Co2 and Co4 via O9 atom, while another μ3-OH− connects Co1, Co3 and Co4 via O7 atom. Four Co(II) ions are connected by five carboxylic groups and two μ3-hydroxyl groups to afford a tetranuclear cobalt cluster [Co4(μ2-COO)3(μ3-COO)2(μ3-OH)2] (Figure 7a). Each tetranuclear cluster as a secondary building unit (SBU) is further linked to five adjacent ones by five TCMB3– spacers, affording a 2D [Co4(TCMB)2(μ3-OH)2]n network (Figure 7b). Two bidentate bpee ligands link the tetranuclear double-chain

cobalt

clusters

(Figure

S2).

to The

form

a

1D

cluster-based

linear 2D

[Co4(TCMB)2(μ3-OH)2]n networks are parallel arranged

(b)

(c)

Figure 8. (a) Coordination structure of 8, and tetranuclear cluster [Co4(μ2-COO)6(μ3-OH)2]. (b) Cluster-based 3D [Co4(TCMB)2(μ3-OH)2]n framework. (c) 3D porous MOF.

and pillared by bpee spacer to construct a 3D porous

Two TCMB3– anions are pentadentate and adopt

coordination polymer (Figure 7c). Twelve lattice water

coordination mode IX (Scheme 2). Each TCMB3– connects six

Co(II)


ions

through

two

bidentate

bridging


η1η1-μ2-carboxylic groups and a monodentate bridging

Scheme 2. Nine Coordination Modes of TCMB3– in 1–8

η0η2-μ2-carboxylic group via O17 or O19 atom to afford a cluster-based (Figure

8b),

3D

[Co4(TCMB)2(μ3-OH)2]n which

differs

M O

the

2D

[Co4(TCMB)2(μ3-OH)2]n network in 7. Two bidentate bpee

M

O M

O

O

I

O

bpee in a methanol-water solvent at slightly different temperature (85, 100 and 120 °C). Their structures are obviously different. Complexes 7 and 8 are two porous MOFs containing different tetranuclear cobalt clusters as SBUs, respectively, the total accessible volumes per unit cell volume are 28.1% and 38.1% calculated by PLATON,46 while the accessible volume of 6 is only 5.1%. Synthesis and Infrared Spectra. Complexes 1–8 were prepared by the hydrothermal reactions of metal acetates with H3TCMB and pyridyl-based ligands 4-abpt/Hpdta/bpee at 85–120 °C. The EtOH–H2O solvent was used in the preparations of 1–5, while MeOH–H2O solvent was used for 6–8. The molar ratios of metal acetates with H3TCMB and N-heterocycles were kept in 4:1:1 for 1–3, in 4:1:2 for 4–5, and in 6:1:2 for 6–8. Complexes 4–8 possess N-heterocyclic auxiliary ligands, whereas 4-abpt only plays an organic base in the preparation of 1–3. Comparing with the preparation of 3D zinc framework of 3, the molar amount of 4-abpt in preparing 4 was increased by double. We harvested a different 2D zinc network of 4, which has 4-abpt auxiliary ligand. In complexes 1–8, H3TCMB is fully deprotonated. Flexible TCMB3– exhibits nine coordination modes, as depicted in Scheme 2. Ether oxygen atoms take part in coordination in modes III, IV and VI, corresponding to complexes 3 and 5. In previously reported nine H3TCMB complexes, only [Cu3(TCMB)2py3(H2O)3·10H2O] complex displays ether oxygen-coordination.42

M

M

O M

M

O

O O

O

O

O

O

O

M

M

M

O

M O

M O

O

O

M

O

III

II

O

M O

M O

O

M O O

O

O M

M O

O

O O

M

M

M

O M

O

O

O

O

O

M O

O

M

O

O

O O M

V O

M

O

O

O

M

O

VII

M

O M

O

O O

M

O

O

M

M O

M

O O

O O

VIII

M O

O

VI

O

O

M

O

O

IV

incorporated into the channels as guest molecules. by the reactions of Co(OAc)2·4H2O with H3TCMB and

M O

O

O

(Figure 8c), where twelve lattice water molecules are Above-mentioned cobalt complexes 6–8 were prepared

M O

M

form a 1D zigzag double-chain (Figure S3), which is structure of 8 is a 3D porous metal-organic framework

M O O

O

ligands link tetranuclear [Co4(COO)6(μ3-OH)2] clusters to different from the 1D linear double-chain in 7. The final

M O

M O

framework

from

Page 10 of 21

M

M M

O M

O

O

O

O

O

IX

M

M

IR spectra of 1−8 exhibit characteristic bands of TCMB3– and N-heterocyclic ligands (Figure S4). Their asymmetric and symmetric stretching vibrations of carboxylic groups appear at about 1597 and 1409 cm–1, respectively. The absence of –COOH characteristic peak near 1700 cm–1 indicates H3TCMB fully deprotonated. Complex 4 shows the N–H stretching vibration of 4-abpt at 3319 cm–1. Complex 5 lacks the N–H characteristic peak near 3300 cm–1, indicates the tetrazolyl of Hpdta deprotonated. Cu(II) complex 2 displays a sharp μ3-O–H stretching vibration band at 3543 cm−1. The bands near 3082, 2890, 1262, 1037, and 781 cm−1 are respectively assigned to ν(Ar−H), ν(−CH2−), ν(C−O), ν(C−C), and γ(Ar−H) vibrations. The C–H out-of-plane bending vibration of pyridyl group appears at about 810 cm−1. Broad band near 3450 cm–1 is assigned to the O–H stretching vibrations of coordinated and/or lattice water. Hydrolysis Controlled Synthesis Strategy and PXRD Study. Generally, deprotonation procedure is important in preparing carboxylic complexes.47 It is noteworthy that Cu(II) complex 2, Zn(II) complex 4, and Co(II) complexes 7 and 8 contain μ3-hydroxyl group, while Zn(II) complex 3 has a μ2-hydroxyl group. This phenomenon indicates partial hydrolysis happened. It is well-known that divalent transition-metal ions are easy hydrolyzed in a neutral aqueous solution. Comparing the precipitation-dissolution equilibrium constants of MII(OH)2 compounds, the Ksp values of Mn2+ (2×10-13) and Cd2+ (7×10-15) are close to the


Page 11 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


value of Co2+ (6×10-15) and remarkably larger than those of Zn2+

(3×10-17)

and

Cu2+

(2×10-20).

Therefore, Cu(2) and

From above experimental results, we have guessed a hydrolysis

reaction

mechanism

(Scheme

3).

With

Zn(3,4) complexes occur partially hydrolysis, whereas

hydrothermal temperature increased, the differences of

Mn(1) and Cd(5) complexes have not hydrolyzed.

Co(II) hydrolysis and coordination resulted in the structural

Previously, four 2D and 3D Cd(II)-TCMB complexes were

diversity of 6–8. Under 85 °C, complex 6 did not hydrolyze

prepared under similar hydrothermal conditions without

and

hydrolysis happened.43 Perhaps Co2+ (Ksp = 6×10-15) locates

[Co3(TCMB)2]n ribbon. When temperature increased to 100

at the critical point of hydrolysis, cobalt complexes 7 and 8

°C, hydrolysis happened. Four Co(II) ions are connected by

happen hydrolysis, whereas cobalt complex 6 does not

two μ3-hydroxyl groups and five carboxylic groups to

hydrolyze. Based on Ksp values of metal hydroxides, the

afford

hydrolysis controlled synthesis strategy is helpful in the

[Co4(μ2-COO)3(μ3-COO)2(μ3-OH)2]. A carboxylic group is

designed synthesis of hydroxyl-containing coordination

uncoordinated. It seems to indicate that the structure of 7 is

polymers and metal-hydroxyl clusters.

an unstable transition state. The tetranuclear clusters are

had

three

a

distinct

isolated

tetranuclear

Co(II)

cobalt

ions

in

cluster

What is interesting is that the cobalt 3D frameworks

linked to form a 2D [Co4(TCMB)2(μ3-OH)2]n network. By

6–8 were prepared under similar reaction conditions with

increased temperature to 120 °C, the unstable tetranuclear

slightly different temperature, respectively at 85, 100 and

cluster was further converted to a more symmetric and

120 °C. Their 3D structures are much different. Complex 6

stable tetranuclear cluster [Co4(μ2-COO)6(μ3-OH)2], here

has no hydroxyl group. Co(II) ions are isolated by large

the six carboxylic groups of two TCMB3– ligands in 8 all

tridentate TCMB3– ligand, while bpee ligands link Co1,

take part in coordination. The 2D [Co4(TCMB)2(μ3-OH)2]n

Co2 and Co3 to form a 1D zigzag chain. Complexes 7 and

network in 7 was also changed to a 3D porous framework

8 have similar formulas, but obvious differences in their 3D

in 8. Previously, Li and coworker have prepared several

frameworks. Complex 7 possesses a hexadentate (mode-I)

MOFs based on metal-hydroxyl tetranuclear clusters.48–50

and a tetradentate (mode-VIII) TCMB3– ligands. One carboxylic

group

in

the

tetradentate

TCMB3–

is

uncoordinated. Two bpee ligands link Co1/Co2 and Co3/Co4 to form two binuclear Co2(bpee) pieces (Figure S2). Two TCMB3– ligands in 8 adopt pentadentate mode (IX). The bpee ligands link Co1, Co2 and Co3 to form a trinuclear Co3(bpee)2 piece (Figure S3), whereas Co4 is coordinated by six oxygens without N-donor.

Scheme 3. Hydrolysis Procedure in Complexes 6–8

Figure 9. PXRD comparison of the products obtained by the hydrothermal reactions at different temperatures. To further explore the effect of the temperature on the preparations of 6–8, we have done a series of hydrothermal reactions from 60 to 140 °C, and obtained different products. As illustrated in Figure 9, the experimental ACS Paragon Plus Environment


Page 12 of 21

PXRD results obtained at 60, 70 and 90 °C are pretty

Thermal Analyses. In order to investigate the thermal

consistent with the simulated pattern of 6 prepared at 85 °C.

stability of 1–8, their thermal analyses (TG-DSC) were

With the increase of temperature, at 100 °C, four new

completed in 20−800 ºC range. The results are shown in

diffraction peaks were discovered below 10º, which

Figure 10 and Figure S7. Complex 1 lost four lattice water

indicate the formation of a new crystal product that is

and four coordinated water molecules in 50−230 °C (obsd

complex 7. At 120 °C, complex 8 was obtained. The

15.6%, calcd 15.9%). Dehydrated compound successively

diffraction peaks were disappeared at 8.56º, 9.72º and

decomposed after 400 °C. Complex 2 lost half lattice water

17.58º, while a new diffraction peak was discovered at

in 50–130 ºC (obsd 1.2%, calcd 1.6%). Dehydrated

7.08º. The product obtained at 110 °C may be a mixture of

compound was stable to 240 °C, and then decomposed

7 and 8. Upon heating to 130 °C, two new diffraction peaks

quickly. Complex 3 lost two lattice water and four

were discovered at 6.36º and 36.7º, and the diffraction

coordinated water molecules in 130−220 °C (obsd 11.8%,

peaks obviously widen, suggesting the low degree of

calcd 11.4%). Dehydrated compound was stable to 330 °C,

crystallization of the product. At 140 °C, a sharp reduction

and then successively decomposed to 800 °C without

of the diffraction peak number was observed in the PXRD

stopping. Complex 4 lost 5.8% weight in 120−300 °C,

pattern, as a consequence of crystal structure collapse or

corresponding to release a lattice water and hydroxyl group

completely hydrolyzed Co(OH)2 powder product formed.

(calcd 5.0%). The intermediate successively decomposed to

These remarkable variations of the PXRD results distinctly

800 °C without stopping. Complex 5 lost two lattice water

indicate the occurrence of crystal complex conversions.

molecules, and a water and an ethanol ligands in 30−170

As we all know, temperature has great influence on hydrolytic reaction. Comparing the complexes 6, 7 and 8,

°C (obsd 9.6%, calcd 13.0%). The intermediate was stable to 300 °C and then successively decomposed.

we find that 6 synthesized at 85 °C has no hydroxyl group. but 7 synthesized at 100 °C has two μ3-hydroxyl groups, and 8 synthesized at 120 °C has two μ3-hydroxyl groups, which is compatible with the above-mentioned PXRD analysis. In consideration of the similar formulas of 7 and 8, we collected the crystals of 7 and mixed them with methanol (4 mL) and water (4 mL). Then the mixture was sealed in a Teflon-lined reactor and heated at 120 °C for three days. From the PXRD pattern of resulting product, it is evident that partial complex 7 has transformed to 8 (Figure S5). This crystal-to-crystal transition procedure indicates that 8 is a more stable complex.

Co(II) complex 6 lost 9.8% weight in 50−140 °C,

Besides, the PXRD patterns of 1–8 have been measured to check their phase purity in the synthesized products. The peak positions of measured PXRD patterns match well with the simulated ones (Figure S6), indicating the crystal structures are truly representatives of the bulk crystalline products. The differences in the peak intensities of 1, 3 and 5 may be owing to the preferred orientation of these sheet crystal samples.

Figure 10. TG curves of complexes 1−8.

corresponding to the removal of a methanol and five water ligands (calcd 8.5%). The intermediate was stable to 260 °C and then successively decomposed. Complex 7 lost 16.5% weight in 40−150 °C, indicating the release of twelve lattice water molecules and two water ligands (calcd 17.0%). Dehydrated compound kept stable to 300 °C and then successively decomposed. Similarly, complex 8 lost 12.2% weight in 20−170 °C, indicating the removal of twelve lattice water molecules and two water ligands (calcd


Page 13 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


17.0%). Comparing the TG curves of 7 and 8 (Figure S7),

η1η1-μ2-carboxylic group can mediate antiferromagnetic

lattice water in 7 is stable to 40 °C, whereas lattice water in

interaction,30 which dominants the magnetic coupling of

8 is slightly unstable, maybe released before 20 °C. The

complex 1. The η1η2-μ3-carboxylic group links Mn2 and

dehydrated compound of 8 kept stable to 310 °C and then

Mn2B via O5−C1B−O3B carboxylic bridge that favors

successively decomposed. Thermal analyses demonstrate

antiferromagnetic interaction. O5-bridging atom links Mn2

the dehydrated compounds of 3, 4, 5, 7 and 8 kept higher

and Mn2A with a Mn2−O5−Mn2A bond angle of

thermal stability to 300 oC.

105.8(1)º.

Magnetic Properties. In the design of molecule-based

Cu(II) complex 2 is an interesting 2D sandwich-like

magnetic materials, the most important factor concerns the

coordination polymer, in which [Cu3(μ3-OH)3]n layer is

connectors between paramagnetic ions. Shorter connector

sandwiched between two organic layers originating from

often brings to stronger magnetic coupling. Magnetic

typical tripodal TCMB3− ligands. Therefore, the magnetic

interactions of transition metal complexes tend to decrease

interaction is limited in the [Cu3(μ3-OH)3]n layer, whereas

in the order: metal oxide/hydroxide > metal cyanide >metal

interaction between layers can be neglected. The χMT value

N-heterocycle.51

Hydroxyl group as a

of complex 2 at 300 K is 1.30 emu K mol−1, which is

monoatomic bridge and carboxylic group as a triatomic

slightly higher than the only-spin value of three isolated

bridge

exchange

Cu(II) ions (1.13 emu K mol−1 with g = 2.0 and S = 1/2).

carboxylic

Upon cooling, the χMT value steadily increases to a

carboxylate > metal can

interaction.

effectively

transmit

Metal-hydroxyl

magnetic

clusters

complexes often exhibit varied magnetic

and

In

maximum of 1.75 emu K mol−1 at 35 K. This phenomenon

this work, complexes 1, 2, 7 and 8 have hydroxyl and

indicates the ferromagnetic coupling between Cu(II) ions

carboxylic groups connected paramagnetic polynuclear

dominates the magnetic properties of complex 2. The

metal

magnetic

inverse magnetic susceptibility curve shows a linear

susceptibilities were measured in the temperature range of

behavior in the 50−300 K range and obeys the

2−300 K. The magnetic data are depicted in Figure 11, as

Curie−Weiss law with C = 1.29 emu K mol−1 and θ = 20.68

the plots of χMT and χM−1 versus T.

K. The positive θ value indicates a ferromagnetic coupling

clusters.

Their

properties.52–54

variable-temperature

For Mn(II) complex 1, the χMT value at 300 K is 12.34

in the [Cu3(μ3-OH)3]n layer. For Cu(II)-hydroxide complex,

emu K mol−1, which is close to the only-spin value of three

it is well-known that ferromagnetic interaction could be

isolated Mn(II) ions (13.14 emu K

mol−1

with g = 2.0 and S

contributed by a smaller Cu–O(H)–Cu bridging angle.56 In

= 5/2). Upon cooling, the χMT value keeps almost a

the [Cu3(μ3-OH)3]n layer, three Cu–O(H)–Cu bond angles

constant value until 88 K, and then decreases in a

around the central hydroxyl O2 atom (Cu1A–O2–Cu1B,

continuous fashion and finally reaches 1.05 emu K

at

Cu1A–O2–Cu1 and Cu1–O2–Cu1B) are 96.8(2)º, 113.7(2)º

2 K. It indicates an antiferromagnetic coupling between

and 126.5(2)º, respectively. The Cu1…Cu1A, Cu1…Cu1B

Mn(II) ions. In the range of 38−45 K, the shake of χMT−T

and Cu1A … Cu1B distances are 3.241(1), 3.747(2) and

curve originates from the trace impurity of manganese

3.156(2) Å, respectively. It is noticed that the dx2−y2

oxides such as ferromagnetic Mn3O4.55 The inverse

magnetic orbital of Cu1 lies on the basal plane (O1A, O2,

magnetic susceptibility curve shows a linear behavior in

O2B and O3) of a square-pyramidal geometry, while the

20−300 K and obeys the Curie−Weiss law χM = C/(T−θ),

dx2−y2 magnetic orbital of Cu1A lies on the basal plane (O1,

yielding C = 12.54 emu K mol−1 and θ = −5.9 K. The

O2, O2C and O3A). Both dx2−y2 magnetic orbitals tend to

negative θ value suggests a weak antiferromagnetic

orthogonality with a dihedral angle of 61.4(1)° (Figure S8).

interaction. In complex 1, the hexadentate

mol−1

ligand

Similarly, the dx2−y2 magnetic orbital of Cu1B lies on the

groups and a

basal plane (O1B, O2D, O2E and O3B), which has a

η1η2-μ3-carboxylic group (mode I). Generally, syn-syn

61.4(1)° dihedral angle with that of Cu1, and parallel to the

possesses two syn-syn

η1η1-μ2-carboxylic

TCMB3−



Page 14 of 21

magnetic orbital of Cu1A with a 2.234 Å distance between planes. Above-mentioned small Cu–O(H)–Cu angle and magnetic

orbital

orthogonality

can

result

in

the

ferromagnetic coupling in complex 2.29 Besides, the decline of χMT below 35 K could be due to antiferromagnetic interaction transmitted by three syn–syn η1η1-μ2-carboxylic groups of TCMB3− ligand (Figure 2b).

[Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O (8) Figure 11. Plots of χMT and χM−1 vs T for 1, 2, 7 and 8. Complexes 7 and 8 are two 3D MOFs, which possess different tetranuclear Co(II) clusters. For complex 7, the χMT value at 300 K is 11.1 emu K mol−1, which is obviously higher than the only-spin value of four isolated [Mn3(TCMB)2(H2O)4]n·4nH2O (1)

Co(II) ions (7.50 emu K mol−1 with S = 3/2, assuming g = 2.0). This is due to the large orbital contribution of Co(II) ion located in an octahedral geometry.51 Upon cooling, the χMT value decreases gradually to a minimum of 0.87 emu K mol−1 at 2 K. This behavior is consistent with dominant antiferromagnetic interaction. The data above 27 K can be fitted to the Curie−Weiss law with C = 13.22 emu K mol−1 and θ = −51.98 K. In complex 7, two distinct TCMB3– ligands adopt coordination mode-I (like Mn complex 1) and mode-VIII. It is easy to transmit antiferromagnetic coupling.

[Cu3(TCMB)(μ3-OH)3]n·0.5nH2O (2)

Three

Co–O(H)–Co

bond

angles

around

μ3-hydroxyl O7 atom (Co1–O7–Co4, Co1–O7–Co3 and Co3–O7–Co4) are 93.5(1)º, 101.4(2)º and 127.9(2)º. The Co1 … Co4, Co1 … Co3 and Co3 … Co4 distances are 3.041(1), 3.175(1) and 3.660(1) Å. The Co–O(H)–Co bond angles and Co…Co distances around μ3-hydroxyl O9 atom are similar. Unlike Cu(II) complex 2, smaller Co–O(H)–Co bond angles do not bring obvious ferromagnetic coupling. For Co(II) complex 8, the χMT value at 300 K is 12.69 emu K mol−1, which is higher than the only-spin value of four isolated Co(II) ions (7.50 emu K mol−1). Upon cooling, the χMT value decreases gradually to 5.19 emu K mol−1 at 13 K, then increases sharply to 7.49 emu K mol−1 at 7 K,

[Co4(TCMB)2(bpee)2(μ3-OH)2(H2O)2]n·12nH2O (7) ACS Paragon Plus Environment

Page 15 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


finally decreases to 3.04 emu K mol−1 at 2 K. From the

enough and overcomes the effect of orbital contribution,

viewpoint of magnetic coupling, this behavior is consistent

leading to the increase of χMT value at 7 K.

with dominant antiferromagnetic interaction in complex 8, accompanied by a weak ferromagnetic coupling at low temperature. The data above 27 K is fitted to the Curie−Weiss law, yielding C = 14.19 emu K mol−1 and θ = −39.99 K. In complex 8, two TCMB3– ligands adopt coordination mode-IX. Each TCMB3– has two bidentate syn-syn η1η1-μ2-carboxylic groups and a monodentate bridging η0η2-μ2-carboxylic group, forming a more symmetric tetranuclear cluster [Co4(TCMB)2(μ3-OH)2]n. The syn-syn η1η1-μ2-carboxylic groups can transmit antiferromagnetic bridging

interaction,

η0η2-μ2-carboxylic

whereas group

monodentate can

mediate

ferromagnetic interaction.30 Three Co–O(H)–Co angles around

μ3-hydroxyl

O16

atom

(Co2–O16–Co4,

Co1–O16–Co4 and Co1–O16–Co2) are 99.0(1)º, 100.0(1)º and 123.1(1)º. The Co2…Co4, Co1…Co4 and Co1…Co2 distances are 3.181(1), 3.150(1) and 3.645(2) Å. The Co–O(H)–Co bond angles and Co … Co distances around μ3-hydroxyl O15 atom are similar. In complex 8, smaller Co–O(H)–Co bond angles and the monodentate bridging η0η2-μ2-carboxylic groups bring a weak ferromagnetic coupling at very low temperature. However, it is difficult to theoretically analyze the magnetic susceptibility data of Co(II) complexes,57,58 because there are strong spin−orbit coupling and highly magnetic anisotropy in Co(II) ion. Vilminot and Kurmoo point out,51 Co(II) is a Kramer’s ion with a considerable spin-orbit coupling. The effective spin is 3/2 at room temperature and could be reduced to 1/2 at low temperature. This effective spin reduction would relate a virtual Weiss constant (θ) of ca. −20 K for one isolated Co(II) ion. This phenomenon can bring out quite complexity to the magnetic properties of Co(II) complexes. If analyzing magnetic property according to the viewpoint of Vilminot and Kurmoo,51 upon cooling, the decrease of χMT value could originate from the spin−orbit coupling of Co(II) ions. There are two comparable interactions of ferromagnetic coupling and orbital contribution in complex 8. In low temperature range, the ferromagnetic coupling is strong

CONCLUSIONS Eight novel coordination polymers and metal-organic frameworks were assembled by a tripodal ether-linked tricarboxylic acid. The tricarboxylate ligand exhibits nine types of coordination modes. These complexes display structural variation with interesting 2D and 3D networks. The results demonstrate that the ether-linked tricarboxylic acid is a good flexible multidentate ligand in constructing coordination polymers. Five complexes contain μ3- and μ2-hydroxyl groups. A hydrolysis controlled synthesis strategy is suggested based on Ksp values of metal hydroxides. Temperature has great influence on the hydrolytic reactions of cobalt complexes 6–8. PXRD study reveals the hydrolysis mechanism. Four complexes present antiferromagnetic and/or ferromagnetic interactions. Their magneto-structural correlations are studied. ASSOCIATED CONTENT Supporting Information Supporting information is available free of charge on the ACS Publications website at DOI: XXXX Bond distances and angles, hydrogen bonds, structural figures, IR spectra, PXRD patterns, and thermal analyses (PDF). Accession Codes CCDC 1888154−1888161 contain the supplementary crystallographic data. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Tel: 86-21-66132803. ORCID Ming-Xing Li: 0000-0003-0000-9876



Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was financially supported by Natural Science Foundation of Shanghai (17ZR1410600, 16ZR1411400) and National Natural Science Foundation of China (21171115). References (1) Kirchon, A.; Feng, L.; Drake, H. F.; Josepha, E. A.; Zhou, H.-C. From Fundamentals to Applications: A Toolbox for Robust and Multifunctional MOF Materials. Chem. Soc. Rev. 2018, 47, 8611–8638. (2) O’Keeffe, M.; Yaghi, O. M. Deconstructing the Crystal Structures of Metal-Organic Frameworks and Related Materials into Their Underlying Nets. Chem. Rev. 2012, 112, 675–702. (3) Lin, Z.-J.; Lü, J.; Hong, M.; Cao, R. Metal–Organic Frameworks Based on Flexible Ligands (FL-MOFs): Structures and Applications. Chem. Soc. Rev. 2014, 43, 5867−5895. (4) Batten, S. R.; Champness, N. R.; Chen, X.-M.; Garcia-Martinez, J.; Kitagawa, S.; Öhrström, L.; O’Keeffe, M.; Suh, M. P.; Reedijk, J. Coordination Polymers, Metal–Organic Frameworks and the Need for Terminology Guidelines. CrystEngComm 2012, 14, 3001−3004. (5) Silva, P.; Vilela, S. M. F.; Tomé, J. P. C.; Paz, F. A. A. Multifunctional Metal–Organic Frameworks: From Academia to Industrial Applications. Chem. Soc. Rev. 2015, 44, 6774−6803. (6) Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M. Topological Analysis of Metal−Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle. Chem. Rev. 2014, 114, 1343−1370. (7) Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chem. Rev. 2012, 112, 933–969. (8) Espallargas, G. M.; Coronado, E. Magnetic Functionalities in MOFs: from the Framework to the Pore. Chem. Soc. Rev. 2018, 47, 533−557. (9) Lustig, W. P.; Li, J. Luminescent Metal–Organic Frameworks and Coordination Polymers as Alternative Phosphors for Energy Efficient Lighting Devices. Coord. Chem. Rev. 2018, 373, 116–147. (10) Burtch, N. C.; Walton, K. S. Modulating Adsorption and Stability Properties in Pillared Metal−Organic Frameworks: A Model System for Understanding Ligand Effects. Acc. Chem. Res. 2015, 48, 2850−2857. (11) Shi, P.-P.; Tang, Y.-Y.; Li, P.-F. Liao, W.-Q.; Wang, Z.-X.; Ye, Q.; Xiong, R.-G. Symmetry Breaking in Molecular Ferroelectrics. Chem. Soc. Rev. 2016, 45, 3811–3827. (12) Qin, L.; Zheng, H.-G. Structures and Applications of Metal–Organic Frameworks Featuring Metal Clusters.

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Table 1. Crystallographic Data and Structural Refinements of Complexes 1–8 complex formula

1

2

C12H17O13Mn1.5

C12H13O12.5Cu3

3 C24H31O25Zn3.5

4 C24H22N6O11Zn2

formula weight

451.66

547.85

948.28

701.21

crystal system

triclinic

trigonal

triclinic

triclinic

space group

P-1

P-3

P-1

P-1

a (Å)

4.6446(16)

8.895(2)

11.390(2)

11.279(8)

b (Å)

13.014(5)

8.895(2)

12.684(2)

11.602(8)

c (Å)

14.321(5)

11.460(5)

12.893(2)

12.022(9)

α (º)

66.416(4)

90

87.979(2)

70.675(9)

β (º)

84.772(4)

90

67.951(2)

65.875(7)

γ (º)

80.582(4)

120

70.430(2)

69.059(8)

V (Å3)

782.3(5)

785.2(5)

1617.9(5)

1309.0(17)

Z

2

2

2

2

Dc (g cm−3)

1.917

2.317

1.947

1.779

μ (mm−1)

1.304

4.099

2.672

1.907

reflections/ unique

4880/ 3452

4811/ 1222

10409/ 7354

8316/ 5845

Rint

0.0266

0.0851

0.0302

0.0207

data/ restraint/ param

3452/ 12/ 259

1222 / 1/ 87

7354/ 18/ 496

5845/ 4/ 391

R1, wR2 [I >2σ(I)]

0.0489, 0.1360

0.0574, 0.1356

0.0480, 0.1151

0.0502, 0.1453

R1, wR2 (all data)

0.0633, 0.1505

0.0883, 0.1537

0.0740, 0.1302

0.0678, 0.1574

GOF on F2

1.102

1.076

1.063

1.065

largest difference in peak and hole (e Å−3) complex

0.714, −0.824

0.859, −1.300

1.918, −0.771

2.625, −0.567

formula

C20H25N5O13Cd2

formula weight

768.25

1439.95

1480.78

1480.78

crystal system

monoclinic

triclinic

triclinic

triclinic

space group

P21/n

P1

P-1

P-1

a (Å)

11.8276(8)

7.488(4)

11.7241(15)

11.887(5)

b (Å)

14.1076(9)

10.006(5)

14.677(2)

12.930(6)

c (Å)

16.5266(11)

23.081(12)

19.290(3)

21.037(9)

α (º)

90

89.617(6)

79.327(2)

103.317(5)

β (º)

104.8590(10)

86.838(6)

82.002(2)

97.498(6)

6

5

C61H62N6O24Co3

7 C48H68N4O34Co4


8 C48H68N4O34Co4


Page 20 of 21

γ (º)

90

70.213(5)

68.331(2)

90.347(5)

V (Å3)

2665.4(3)

1624.7(14)

3022.2(7)

3117(2)

Z

4

1

2

2

Dc (g cm−3)

1.914

1.472

1.627

1.578

μ (mm−1)

1.670

0.841

1.179

1.143

reflections/ unique

16337/ 6166

10297/ 8624

19279/ 13544

19783/ 13966

Rint

0.0185

0.0184

0.0329

0.0224

data/restraint/param

6166/ 9/ 368

8624/ 18/ 872

13544/ 6/ 823

13966/ 6/ 817

R1, wR2 [I >2σ(I)]

0.0324, 0.0871

0.0410, 0.1061

0.0629, 0.1554

0.0541, 0.1520

R1, wR2 (all data)

0.0409, 0.0930

0.0621, 0.1220

0.1078, 0.1847

0.0810, 0.1695

GOF on F2

1.047

1.019

1.028

1.091

largest difference in peak and hole (e Å−3)

1.510, −0.997

0.747, −0.346

1.346, −0.731

0.895, −0.672


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For Table of Contents Use Only

Hydrolysis Controlled Synthetic Strategy and Structural Variation of Hydroxyl-Metal Clusters and Metal-Organic Frameworks Based on Tripodal Ether-Linked 1,3,5-Tris(carboxymethoxy)benzene Jia-Yao Zhang, Xue-Li Ma, Zhao-Xi Wang, Xiang He, Min Shao, and Ming-Xing Li* Eight coordination polymers were assembled by a tripodal ether-linked tricarboxylate ligand that exhibits nine types of coordination modes. The ether-linked tricarboxylic acid is a good flexible multidentate ligand in constructing various coordination networks. Five complexes have μ3- and μ2-hydroxyl groups. A hydrolysis controlled synthesis strategy is suggested based on Ksp values of metal hydroxides. Temperature has great influence on the hydrolytic reactions of cobalt complexes 6–8. PXRD study reveals the hydrolysis mechanism. Four complexes present antiferromagnetic and/or ferromagnetic interactions.


Hydrolysis Controlled Synthetic Strategy and Structural Variation of

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