Spiro-containing platinum(II) emitters with tunable emission energies and syntheses thereof
An asymmetric tetradentate metal complex of a N{circumflex over ( )}C{circumflex over ( )}C{circumflex over ( )}N comprising tetradentate ligand has a metal connected to binding sites which are connected to each other via three or four covalent bonds that can be either single or double bonds with bridging linkers reside between C{circumflex over ( )}C and C{circumflex over ( )}N moieties. These linkers result in three-dimension metal complexes with distorted square planar geometries. The four donor atoms coordinate to a metal center. Upon metal binding a 5-6-6 membered metallocycle is formed upon chelation including a first nitrogen donor bond, a first metal-carbon bond, a second metal-carbon bond, and a second nitrogen donor bond. The light emission from these metal complexes can be tuned by the ligand structure over the entire visible spectrum.
1. An asymmetric metal complex, comprising the structure:
where M is Pt, Ir, W, Fe, Ru, Ni, Cu, Au or Zn; where Ar 1 is a substituted or unsubstituted aromatic or heteroaromatic ring where X is N or other electron pair donor;
is
and forms a spiro unit with C a , where C a is a bridging atom and can be independently: nitrogen, carbon, boron, phosphorus, silicon, sulfur, or a combination thereof and O b is a bond, O, S, NR 17 , B R 17 , PR 17 , CR 17 R 18 , or SiR 17 R 18 ; where O a is O, S, NR 19 , B R 19 , PR 19 , CR 19 R 20 , or SiR 19 R 20 ; where N 1 , N 2 and N 4 are independently unsubstituted or substituted boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium and n is 1 to 3; where N 3 is carbon, boron, nitrogen, oxygen, silicon, phosphorous, sulphur or selenium; and the ring containing N 1 , N 2 , N 3 and N 4 is a saturated, unsaturated or aromatic ring; where R 1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group and where a pair of adjacent R groups can independently form a 5-8 membered aryl or arylalkyl ring which may be interrupted one or more times with O, S, N, or NR 21 ; and where R 17 , R 18 , R 19 , R 20 , and R 21 are independently alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, haloalkyl, arylalkane or arylalkene.
2. The metal complex according to claim 1 , wherein Ar 1 is an aromatic ring or heteroaromatic ring which can be substituted or unsubstituted; wherein X is coordinated to the central metal atom, M.
3. The metal complex according to claim 1 , wherein N 1 , N 2 and N 4 are independently boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium; wherein N 3 is independently carbon coordinated to the central metal atom, M; and the ring containing N 1 , N 2 , N 3 and N 4 is a saturated, unsaturated or aromatic ring; wherein R 1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; wherein each of n and m are independently an integer 1, 2, or 3.
4. The metal complex according to claim 1 , wherein
is
wherein R 9 -R 16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group; and each pair of adjacent R groups of R 9 -R 16 can be independently form 5-8 membered ring(s) with 2 or 4 carbon atoms in the phenyl ring(s); wherein O b is a bond, nitrogen, carbon, boron, phosphorus, silicon, oxygen, sulfur.
5. The metal complex according to claim 1 , wherein the M is Pt.
6. The metal complex according to claim 1 , wherein R 2 -R 8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene.
7. The metal complex according to claim 1 , wherein C a can be independently nitrogen, carbon, boron, phosphorus, silicon, oxygen, sulfur or a combination thereof.
8. The metal complex according to claim 1 , wherein the metal complex has one of the following structures:
9. A tetradentate ligand, comprising the structure:
where Ar 1 is a substituted or unsubstituted aromatic or heteroaromatic ring where X is N or other electron pair donor;
is
and forms a spiro unit with C a , where C a is carbon or silicon and O b is a bond, O, S, NR 17 , B R 17 , PR 17 , CR 17 R 18 , or SiR 17 R 18 , where O a is O, S, NR 19 , B R 19 , PR 19 , CR 19 R 20 , or SiR 19 R 20 , where N 1 , N 2 and N 4 are independently unsubstituted or substituted boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium and n is 1 to 3; where N 3 is carbon, boron, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium; and the ring containing N 1 , N 2 , N 3 and N 4 is a saturated, unsaturated or aromatic ring; where R 1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group and where a pair of adjacent R groups can independently form a 5-8 membered aryl or arylalkyl ring which may be interrupted one or more times with O, S, N, or NR 21 ; and where R 17 , R 18 , R 19 , R 20 , and R 21 are independently alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, haloalkyl, arylalkane or arylalkene, and wherein when Ar 1 is pyridyl or isoquinyl or R 1 is halogen then at least one of R 10 and R 15 is not t-butyl when R 9 , R 11 , R 12 , R 13 , R 14 , and R 16 are hydrogen.
10. The tetradentate ligand according to claim 9 , wherein the tetradentate ligand has one of the following structures:
11. A method of preparing a metal complex, comprising:
providing a tetradentate ligand according to claim 9 ;
providing a metal salt comprising Pt, Ir, W, Fe, Ru, Ni, Cu, Au, or Zn; and
reacting the tetradentate ligand with the metal salt.
12. A method of preparing a metal complex of a ligand core, comprising:
reacting the ligand core with metal salt in presence of tetra-n-butyl ammonium salt,
where the structure of the metal complex is the following structure:
Where M is Pt, Ir, W, Fe, Ru, Ni, Pd, Cu, Au, or Zn and the structure of the ligand core is the following structure:
where Ar 1 is a substituted or unsubstituted aromatic or heteroaromatic ring where X is N or other electron pair donor;
is
and forms a spiro unit with C a , where C a is carbon or silicon and O b is a bond, O, S, NR 17 , B R 17 , PR 17 , CR 17 R 18 , or SiR 17 R 18 , where O a is O, S, NR 19 , B R 19 , PR 19 , CR 19 R 20 , or SiR 19 R 20 ; where N 1 , N 2 and N 4 are independently unsubstituted or substituted boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium and n is 1 to 3; where N 3 is carbon, boron, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium; and the ring containing N 1 , N 2 , N 3 and N 4 is a saturated, unsaturated or aromatic ring; where R 1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group and where a pair of adjacent R groups can independently form a 5-8 membered aryl or arylalkyl ring which may be interrupted one or more times with O, S, N, or NR 21 ; and where R 17 , R 18 , R 19 , R 20 , and R 21 are independently alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, haloalkyl, arylalkane or arylalkene.
13. The method according to claim 12 , wherein the metal salt is potassium tetrachloroplatinate(II), bis-dimethylsulfide platinum(II) dichloride, cis-dichlorobis(dimethyl sulfoxide)platinum(II), dichloro(1,5-cyclooctadiene)platinum(II), or potassium tetrachloroplatinate(II).
14. The method according to claim 12 , wherein reacting is refluxing in a solvent.
15. The method according to claim 14 , wherein the solvent is acetic acid or a mixture of acetic acid and chloroform or methylene chloride.
16. A light-emitting device, comprising at least one metal complex according to claim 1 .
17. The light-emitting device according to claim 16 , wherein the device comprises at least one organic light-emitting diode (OLED).