A tetrahedral coordination cage bad on p -tert -butylthiacalix[4]arene and 5-sulfoisophthalic acid
Mei Liu a ,b ,Shangchao Du a ,b ,Yanfeng Bi a ,Wuping Liao a ,1
a
dawnedState Key Laboratory of Rare Earth Resource Utilization,ERC for the Separation and Puri fication of REs and Thorium,Changchun Institute of Applied Chemistry,Chine Academy of Sciences,Changchun 130022,China b
University of Chine Academy of Sciences,Beijing 100049,China
a b s t r a c t
a r t i c l e i n f o Article history:
Received 9November 2013Accepted 6January 2014
Available online 15January 2014Keywords:
Cage compounds Calixarenes Cobalt
ttm
Crystal engineering Magnetic property
wgqA new cobalt –thiacalix[4]arene compound [(CH 3)4N]2{[Co 4Cl(TC4A)(CH 3OH)]4(SIP)4(HCOO)2}(CIAC-111)was synthesized by the solvothermal reaction of CoCl 2·6H 2O,p -tert -butylthiacalix[4]arene (H 4TC4A)and 5-sulfoisophthalic acid sodium salt (NaH 2SIP).It is featured with a tetrahedral coordination cage with four Co 4-TC4A shuttlecock-like subunits as the vertices and four SIP molecules as the tripod linkers located on the triangu-lar faces.The structure and coordination mode of SIP play a crucial role in the formation of such a cage.The magnetic property of this compound was examined.
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Due to their intriguing structures and well-de fined cavities,high symmetry and stability,and rich physical and chemical properties,high-nuclearity coordination cages have attracted increasing attention [1].During the past decade,some coordination nanocages bad on calixarene/metal –calix
arene entities as the vertices have also been re-ported [2].Recently,we reported a ries of calixarene-bad octahedral {Co 24}coordination nanocages with Co 4-calix subunits as the vertices,which were bridged by rigid tripodal aromatic tricarboxylic acids such as 1,3,5-benzenetricarboxylic acid (H 3BTC)and 4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid (H 3BTB)through a [6+8]condensation [3].Dai and Wang also obtained veral similar cage compounds by this strate-gy [4].However,Hong structed another octahedral nanocage with a linear dipodand 1,4-benzene dicarboxylic acid by a [6+12]condensation [5].A tetragonal prismatic {Co 32}coordination cage was obtained with the in situ-generated 1,3-bis(2H-tetrazol-5-yl)benzene as a tetrapod linker [6].2D aggregates incorporating pre-designed metal –calixarene coordination cages were obtained with isonicotinic acid [7].It is found that the shuttlecock-like Co 4-calix is a stable building block in the structures.Except the cage-like structures,the Co 4-calix condary building units (SBUs)can also be bridged into the isolated polynuclear clusters,squares,metallamacrocycle and wave-like chains or belts by different ligands or a same ligand with a different coordina-tion mode [8–11].Our interest is to construct novel calixarene-bad coordination cages through bridging the SBUs with a ligand having different coordination modes.Here we choo p -tert -butylthiacalix[4]
arene (H 4TC4A)as the calixarene source and 5-sulfoisophthalic acid (H 3SIP)as the linker,and a no
vel tetrahedral nanocage [(CH 3)4N]2{[Co 4Cl(TC4A)(CH 3OH)]4(SIP)4(HCOO)2}(CIAC-111)was obtained.On a clo examination,one can find that the H 3SIP molecule also acts as a tripodal ligand but it has a coordination mode different from H 3BTC in CIAC-101[3a],which leads to the formation of such tetrahedral coor-dination cages (Scheme 1).
CIAC-111crystallizes in a monoclinic system with space group C 2/c .A TC4A molecule adopting a cone conformation bonds a square Co 4cluster core through four phenolic oxygen atoms and four bridge sulfur atoms to form a shuttlecock-like Co 4-TC4A SBU with a bonded μ4-Cl −anion at the lower rim.All Co cobalt ions are six-coordinated by two phenolic oxygens,one sulfur,one μ4-Cl −and two other oxygens from different donors (i.e.,SIP /methanoic acid/methanol)(Scheme 1f).Bond valence sum (BVS)calculations suggest that all the cobalt cations are divalent,which is also con firmed by magnetic measurement.
雨痕Four Co 4-TC4A SBUs are jointed together by four SIP molecules and two methanoic acids into a discrete tetrahedral cage (Fig.1),in which the Co 4-TC4A SBUs reside on the vertices of the tetrahedron.Methanoic acid found in the structure can be assigned to the oxidation of CH 3OH.The cavity inside the cage is occupied by a (CH 3)4N +counter ion so that there is nearly no pores for this structure,which is con firmed by the N 2sorption isotherm at 77K (Fig.S1).The BET surface area
was cal-culated to be 26.36m 2g −1.The discrete nanocages are stacked through molecular interactions into a 3D supramolecular structure and the inter-stices are presumably occupied by some disordered counter cations and solvent molecules (i.e.,CHCl 3and/or CH 3OH)who contribution was subtracted from the diffraction data by the SQUEEZE command in PLATON [12].
bopetInorganic Chemistry Communications 41(2014)96–99
E-mail address:wpliao@ciac.ac (W.Liao).1
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dx.doi/10.1016/j.inoche.2014.01.009
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SIP can be thought to form by replacing one carboxyl group of BTC by a sulfonic group.Although it also acts as a tripodal linker,no octahedral nanocage similar to CIAC-101[3a]was obtained but a tetrahedral one (Fig.1,left),which would be attributed to the different coordination modes of SIP and
BTC.As shown in Scheme 1,both SIP and BTC bond six metal atoms but all the Co \O bonds concerned BTC just deviate slightly from the aromatic plane while two concerned the sulfonic group of SIP deviate heavily (the angle between the bond direction and the aromatic plane being of 104.1°).The coordination mode of SIP
is crucial to the formation of tetrahedral coordination cage.This mode is helpful to keep the stable Co 4-TC4A SBUs by keeping similar angles between opposite Co \O bonds as tho in CIAC-101(Fig.S2)and pro-tect the tetrahedral cage from collap.
It is also found that the Co \O sulfonic distances fall in the range of 2.07–2.11Åwhile the Co \O carboxyl distances are in the range of 2.00–2.03Å,that is,the bond lengths of Co \O sulfonic are longer than tho of the Co \O carboxyl bond.It can be deduced that the carboxyl groups exhibit stronger af finity towards the cobalt atoms than the sul-fonic groups.If there are enough SIP ligands in the system,the carboxyl groups will preferentially bond the cobalt cations and the sulfonic groups will keep non-coordinated.To verify this hypothesis,another experiment with incread amount of NaH 2SIP was performed under the similar conditions.As expected,a novel compound containing non-coordinated sulfonic groups was obtained (which will be reported elwhere).It has a window frame-like square structure similar to CIAC-201and -202with 1,3-H 2BDC and 2,6-pyridine dicarboxyl
ic acid [9],in which four Co 4-TC4A SBUs were bridged by eight SIP molecules through their carboxylic groups and the sulfonic groups are kept non-coordinated.
In order to evaluate thermal stability of CIAC-111,the thermal be-havior of this compound was studied.As shown in Fig.2,the TG data indicate that the cage structure of CIAC-111is thermally stable and does not decompo until 325°C.The TG curve keeps steady until heating to 690°C.Energy dispersive X-ray spectroscopy (EDS)analysis on the residue reveals that the Co:O ratio is 50.07:46.68,which suggests that the final residue was CoO.A systematic low-magni fication scanning electron microscope (SEM)investigation showed that the residues are compod of some conglutinated nanoparticles (Fig.2,right),which also supports that the metal –organic complexes can act as outstanding precursors for the nanomaterials [13].
Magnetic susceptibility of CIAC-111was performed in the 2–300K temperature range in an applied field of 1kOe as shown in Fig.3.The χM T value decreas gradually from 35.41cm 3K mol −1at 300K to 0.73cm 3K mol −1at 2K.At 300K,the experimental χM T value is higher than the expected value (30.0cm 3K mol −1)for sixteen spin-only high-spin Co II ions (S =3/2,g =2,C =1.875cm 3K mol −1)due to a strong orbital contribution of the Co II ions.The reciprocal molar susceptibility in 50–300K follows the Curie –Weiss Law of 1/χM =(T −θ)/C with C =39.48cm 3K mol −1and θ=−33.62K.T
he negative Weiss constant (θ)value suggests an antiferromagnetic interaction between the metal centers and/or the spin –orbit coupling effect of Co II .It is consistent with other compounds built from Co 4-TC4A SBUs.[3a,10]
In summary,we have successfully synthesized a novel discrete calixarene-bad coordination cage by introducing 5-sulfoisophthalic acid into the Co-TC4A system.Four SIP molecules and two methanoic acids bridge the Co 4-TC4A SBUs into a tetrahedral arrangement.It
is
Scheme 1.Molecular structures of BTC (a)and SIP (b),coordination modes of BTC (c)and SIP (d),the coordination of a Co 4-TC4A SBU by BTC (e)and SIP (f),and the formation of octahedral cage (g)and tetrahedral cage
(h).
Fig.1.Molecular structures of CIAC-111(left)and CIAC-101[3a](right).The truncated cones denote the Co 4-TC4A SBUs.
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M.Liu et al./Inorganic Chemistry Communications 41(2014)96–99
found that the structure and coordination mode of SIP play a crucial role in the formation of such a cage.Some different cages might be obtained if the carboxylic groups of the linker are substituted by other functional groups.
Acknowledgments
This work was supported by National Natural Science Foundation of China (Nos.20971119,21221061,51222404and 91026024).Appendix A.Supplementary material
CCDC-959852contains the supplementary crystallographic data for this paper.The data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwdc.cam.ac.uk/d
ata_request/cif .Supplementary data to this article can be found online at dx.doi/10.1016/j.inoche.2014.01.009.References
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Fig.3.Plots of χM T vs T and 1/χM vs T for CIAC-111in a 1000Oe field.The solid line shows the Curie –Weiss fitting.
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