Homochiral three-dimensional noncentrosymmetric lanthanide coordination polymers directed by chiral linkers: syntheses, crystal structures, and optical properties

Abstract

Crystals of six enantiomorphic lanthanide-organic coordination polymers, [Ln2((R,R)-TBA)2((R,R)-HTBA)2(H2O)2]·7H2O [Ln(R)] and Ln2((S,S)-TBA)2((S,S)- HTBA)2(H2O)2]·7H2O [Ln(S)] (Ln = La, Ce, and Pr; TBA = 1,3,5-triazin-2(1H)-one-4,6- bis(alanyl)), have been grown through solvothermal reactions. The...

Chiral Ligand‐Driven Systematic Synthesis of Coordination Polymers with Non‐centrosymmetric Structures

“…In this Concept article, we suggest a systematic method to synthesize coordination polymers (CPs) with macroscopic NCS structures by using chiral organic ligands as structure directing agents. We have synthesized a series of novel enantiomorphic CPs with robust chiral organic ligands, in which interesting materials’ properties along with rich structural chemistry have been observed [4a–c] . We believe that the findings successfully suggest a systematic approach toward discovering functional solid state materials with macroscopic NCS structures with excellent NLO properties.…”

“…Homochiral CPs introduced in this Concept article have been obtained by using two types of novel organic ligands. Specifically, the chiral linkers were initially synthesized via nucleophilic aromatic substitution reactions using L‐ or D‐alanine and rigid organic templates such as 1,3,5‐triazin‐2(1H)‐one‐4,6‐bis(alanyl)) ( TBA ) [4b,c] or ( S , S or R , R )‐2,2′‐(isophthaloylbis(azanediyl))dipropionic acid ([( S )‐2] or [( R )‐2]) [4a] …”

“…[Ln 2 (( R , R )‐ TBA ) 2 (( R , R )‐H TBA ) 2 (H 2 O) 2 ] ⋅ 7 H 2 O and [Ln 2 (( S , S )‐ TBA ) 2 (( S , S )‐H TBA ) 2 (H 2 O) 2 ] ⋅ 7 H 2 O (Ln=La 3+ , Ce 3+ , and Pr 3+ ) have been synthesized by solvothermal reactions [4c] . Here, the chirality of lanthanide‐based organic coordination polymers (Ln‐CPs) was induced by the introduced TBA ligands as chiral templates.…”

(R)- and (S)-[C8H10NO3]2[NbOF5]: noncentrosymmetric niobium oxyfluorides with large optical anisotropy

“…[30][31][32] Recently, our group has been quite successful in systematically synthesizing a series of novel NCS organic-inorganic hybrid materials or coordination compounds by utilizing chiral structure-directing agents or chiral ligands. [33][34][35][36][37] We found that the crystals exhibit large birefringence (Δn exp ) of 0.19-0.199@589.3 nm; thus, the origin of the large optical anisotropy is elucidated through a more detailed analysis. The newly synthesized materials also exhibit large band gaps along with strong stability in various solvents.…”

“…30–32 Recently, our group has been quite successful in systematically synthesizing a series of novel NCS organic–inorganic hybrid materials or coordination compounds by utilizing chiral structure-directing agents or chiral ligands. 33–37 In this work, we have successfully grown huge crystals of two NCS hybrid niobium oxyfluorides, ( R )-[C 8 H 10 NO 3 ] 2 [NbOF 5 ] [( R )-Nb] and ( S )-[C 8 H 10 NO 3 ] 2 [NbOF 5 ] [( S )-Nb], by introducing carefully controlled chiral templates, 4-hydroxy- d -(−)-2-phenylglycine [( R )-HPG] and 4-hydroxy- l -(+)-2-phenylglycine [( S )-HPG]. We found that the crystals exhibit large birefringence (Δ n exp ) of 0.19–0.199@589.3 nm; thus, the origin of the large optical anisotropy is elucidated through a more detailed analysis.…”