title: Homochiral D4-symmetric metal-organic cages from stereogenic Ru(II) metalloligands for effective enantioseparation of atropisomeric molecules.
abstract: Absolute chiral environments are rare in regular polyhedral and prismatic architectures, but are achievable from self-assembly of metal-organic cages/containers (MOCs), which endow us with a promising ability to imitate natural organization systems to accomplish stereochemical recognition, catalysis and separation. Here we report a general assembly approach to homochiral MOCs with robust chemical viability suitable for various practical applications. A stepwise process for assembly of enantiopure ΔΔΔΔΔΔΔΔ- and ΛΛΛΛΛΛΛΛ-Pd6(RuL3)8 MOCs is accomplished by pre-resolution of the Δ/Λ-Ru-metalloligand precursors. The obtained Pd-Ru bimetallic MOCs feature in large D4-symmetric chiral space imposed by the predetermined Ru(II)-octahedral stereoconfigurations, which are substitutionally inert, stable, water-soluble and are capable of encapsulating a dozen guests per cage. Chiral resolution tests reveal diverse host-guest stereoselectivity towards different chiral molecules, which demonstrate enantioseparation ability for atropisomeric compounds with C2 symmetry. NMR studies indicate a distinctive resolution process depending on guest exchange dynamics, which is differentiable between host-guest diastereomers.
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Kai
authors.initials: K
authors.lastname: Wu
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Kang
authors.initials: K
authors.lastname: Li
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Ya-Jun
authors.initials: YJ
authors.lastname: Hou
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Mei
authors.initials: M
authors.lastname: Pan
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Lu-Yin
authors.initials: LY
authors.lastname: Zhang
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors.forename: Ling
authors.initials: L
authors.lastname: Chen
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.|State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
authors.forename: Cheng-Yong
authors.initials: CY
authors.lastname: Su
references.citation: Org Lett. 2000 May 4;2(9):1255-7
references.pmid: 10810721
references.citation: Chemistry. 2002 Jun 17;8(12):2679-83
references.pmid: 12391644
references.citation: J Am Chem Soc. 2003 Apr 30;125(17):5193-8
references.pmid: 12708871
references.citation: J Am Chem Soc. 2004 Mar 31;126(12):3674-5
references.pmid: 15038695
references.citation: Dalton Trans. 2004 May 7;(9):1277-83
references.pmid: 15252618
references.citation: Chem Commun (Camb). 2005 Oct 7;(37):4647-9
references.pmid: 16175279
references.citation: J Am Chem Soc. 2006 Feb 1;128(4):1324-33
references.pmid: 16433551
references.citation: Chem Commun (Camb). 2006 Nov 28;(44):4644-6
references.pmid: 17082870
references.citation: Inorg Chem. 2007 Jun 25;46(13):5354-60
references.pmid: 17530753
references.citation: J Am Chem Soc. 2007 Dec 12;129(49):15354-63
references.pmid: 18020339
references.citation: J Am Chem Soc. 2008 Jul 2;130(26):8160-1
references.pmid: 18540605
references.citation: J Am Chem Soc. 2008 Aug 6;130(31):10058-9
references.pmid: 18613672
references.citation: J Am Chem Soc. 2009 Feb 11;131(5):1896-902
references.pmid: 19154111
references.citation: Acc Chem Res. 2009 Oct 20;42(10):1554-63
references.pmid: 19555073
references.citation: Acc Chem Res. 2009 Oct 20;42(10):1650-9
references.pmid: 19591461
references.citation: Angew Chem Int Ed Engl. 2009;48(40):7343-5
references.pmid: 19739168
references.citation: Chemistry. 2010 Mar 15;16(11):3318-25
references.pmid: 20187047
references.citation: Angew Chem Int Ed Engl. 2010 Jun 1;49(24):4121-4
references.pmid: 20458719
references.citation: Chemistry. 2010 Nov 2;16(41):12328-41
references.pmid: 20938934
references.citation: J Am Chem Soc. 2010 Nov 17;132(45):16256-64
references.pmid: 20977233
references.citation: Angew Chem Int Ed Engl. 2011 Apr 4;50(15):3479-83
references.pmid: 21394866
references.citation: J Am Chem Soc. 2011 Aug 17;133(32):12402-5
references.pmid: 21749065
references.citation: J Am Chem Soc. 2011 Aug 31;133(34):13652-60
references.pmid: 21790184
references.citation: Angew Chem Int Ed Engl. 2012 Feb 6;51(6):1464-8
references.pmid: 22213279
references.citation: Chem Rev. 2012 Apr 11;112(4):2015-41
references.pmid: 22251425
references.citation: J Am Chem Soc. 2012 May 16;134(19):8042-5
references.pmid: 22545574
references.citation: J Am Chem Soc. 2012 May 16;134(19):8070-3
references.pmid: 22548529
references.citation: Angew Chem Int Ed Engl. 2012 Jul 2;51(27):6681-5
references.pmid: 22674771
references.citation: Angew Chem Int Ed Engl. 2012 Jul 9;51(28):6882-5
references.pmid: 22684909
references.citation: J Am Chem Soc. 2012 Sep 19;134(37):15528-37
references.pmid: 22916838
references.citation: Chem Soc Rev. 2013 Feb 21;42(4):1728-54
references.pmid: 23032789
references.citation: Chem Rev. 2013 Jan 9;113(1):734-77
references.pmid: 23121121
references.citation: J Am Chem Soc. 2013 Mar 6;135(9):3371-4
references.pmid: 23428093
references.citation: Chemistry. 2013 Apr 8;19(15):4767-75
references.pmid: 23436252
references.citation: J Am Chem Soc. 2013 May 8;135(18):7039-46
references.pmid: 23544861
references.citation: J Am Chem Soc. 2013 Dec 18;135(50):18802-5
references.pmid: 24283463
references.citation: Angew Chem Int Ed Engl. 2014 Feb 3;53(6):1693-8
references.pmid: 24453210
references.citation: J Am Chem Soc. 2014 Mar 26;136(12):4456-9
references.pmid: 24611560
references.citation: Chemistry. 2014 May 19;20(21):6455-61
references.pmid: 24710843
references.citation: Acc Chem Res. 2014 Jul 15;47(7):2063-73
references.pmid: 24793652
references.citation: Angew Chem Int Ed Engl. 2014 Jul 7;53(28):7228-32
references.pmid: 24863541
references.citation: Nat Mater. 2014 Oct;13(10):954-60
references.pmid: 25038731
references.citation: Chem Commun (Camb). 2014 Sep 28;50(75):10979-82
references.pmid: 25096332
references.citation: Chemistry. 2014 Sep 22;20(39):12483-92
references.pmid: 25111071
references.citation: Angew Chem Int Ed Engl. 2014 Oct 27;53(44):11818-21
references.pmid: 25124842
references.citation: Angew Chem Int Ed Engl. 1999;38(8):1018-33
references.pmid: 25138490
references.citation: Chem Commun (Camb). 2015 Mar 4;51(18):3804-7
references.pmid: 25649958
references.citation: Angew Chem Int Ed Engl. 1999 Feb 1;38(3):302-322
references.pmid: 29711653
references.citation: Angew Chem Int Ed Engl. 2001 Jan 5;40(1):157-160
references.pmid: 29711939