Whatis claimed is:
`1.
`
`Attorney Docket No. UDC-1712P (376.0047P)
`
`A compound comprisingafirst ligand La ofFormule I:CL.
`1k!oS
`
`a‘
`
`’
`
`wherein moicty A is a heterocyclic ring comprisingat least 7 ring atoms selected from the group consisting of C, Si, B, O,
`
`S, and N;
`wherein moiety B is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
`wherein X! to X4 are each independently C or N;
`wherein Z! is C or N;
`wherein a is 0 or 1;
`wherein K!is a direct bond, O, or S;
`wherein Z! is C if K! is O or S;
`wherein L! is a direct bond or selected from the group consisting of O, S, Se, NR, BR, BRR’, PR, CR, C=O, C=S, C=NR,
`C=CRR’, CRR’, SO, SOn, SiRR’, GeRR’, and P(O)R;
`wherein each of R“, and R® independently represents mono to the maximum allowable substitution, or no substitution;
`wherein each R, R’. R4, and R® is independently a hydrogenor a substituent selected fromthe group consisting of
`hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalky1, bory], arylalkyl, alkoxy, aryloxy, amino,
`silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile,
`isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;
`wherein La is coordinated to a metal M;
`wherein M is selected from the group consisting of lr, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu;
`wherein the bond between ring A and M is a carbene bond;
`wherein La may be joined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand;
`whereinif M is Pd or Pt, moiety A comprises at least 7 ring atoms, La is comprised by a tetradentate ligand, and X!is not
`joined to a cyclohexyl group; and
`whereinif M is Os, Ir, Cu, Ag, or Au, moiely A comprises al least 8 ring atoms.
`wherein any two substituents may be joined or fused to form a ring.
`The compoundof claim 1, wherein each R, R’, R4, and R®? is independently a hydrogenor a substituent selected fromthe
`group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino,silyl, bory], alkenyl,
`cycloalkenyl, heteroalkeny], aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
`The compoundof claim | or 2, wherein at least one of X! and X? are N.
`The compoundof any of claims 1-3, wherein both of X! and X? are N.
`The compoundof any of claims 1-4, wherein at least one of X° and X* are C.
`The compound of any of claims 1-5, wherein both of X? and X? are C.
`The compoundof any of claims 1-6, wherein Ring A comprisesat least 8 ring atoms.
`The compoundof any of claims 1-7, wherein Ring A comprisesat least 9 ring atoms.
`The compoundof any of claims 1-8, wherein Ring A comprisesat least 10 ring atoms.
`The compoundof any of claims 1-9, wherein Ring A comprisesat least 11 ring atoms.
`The compound of any of claims 1-10, wherein Ring B is a 6-membered carbocyclic ring.
`The compoundofany of claims 1-11, wherein Ring B is an aromatic 6-memberedcarbocyclic or heterocyclic ring.
`The compoundof any of claims 1-12, wherein Z is N.
`The compoundof any of claims 1-13, wherein L' is a direct bond.
`The compoundof any of claims 1-14, wherein K! is a direct bond.
`The compound of any of claims 1-15, wherein Ring A is fused to at least two six-membered aromatic rings.
`The compound of any of claims 1-16, wherein Ring A is fused to at least three six-membered aromatic rings.
`The compound of any of claims 1-17, wherein Ring A compriscsat least three hetcro atoms.
`The compoundof any of claims 1-18, wherein the compound comprisesat least one carbazole group.
`The compoundof any one of claims 19, wherein the ligand La is selected from the group consisting of the structures of
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`

`Attorney Docket No. UDC-1712P (376.0047P)
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`21.
`
`22,
`
`23.
`
`24,
`
`25.
`
`26.
`
`27.
`
`29.
`
`30.
`
`LIST A as defined herein, wherein each of RA“, and RP” independently represents mono to the maximum allowable
`substitution, or no substitution; wherein each R44, RPP, R*, RY and R4 is independently selected from the list consisting of
`the structures of LIST B as defined herein.
`The compoundof any one of claims 1-20, wherein the ligand La is selected from the group consisting of the structures of
`LIST C as defined herein; wherein /, 7, and k, are each independently an integer from 1 to 135, wherein R1 to R135 have
`the structures as defined in TABLE | herein.
`The compound of any one of claims 1-21, wherein the ligand La is selected from the group consisting of the structures of
`LIST D as defined herein.
`The compound of any one of claims 1-22, wherein the compound has a formula of
`M(La)p(Le)q(Lc)r wherein Lg and Le are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; ris 0, 1, or 2;
`and p+q+ris the oxidation state of the metal M.
`The compound of claim 23, wherein the compoundhas a formula selected from the group
`consisting of Ir(La)s, Ir(La)(Le)2, 1r(La)o(Le), Ir(La)2(Lc), and Tr(La)(Le)(Lc); and wherein La,
`Ls, and Lc are different from each other.
`The compoundof claim 23 or claim 24, wherein Le is a substituted or unsubstituted phenylpyridine, and Lc is a substituted
`or unsubstituted acetylacetonate.
`The compoundof claim 23, wherein the compound has a formula of Pi(La)(Le); and
`wherein La and Ls can be sameordifferent.
`The compound of claim 26, wherein La and Le are comected to forma tetradentate ligand.
`The compound of any one of claims 23-27, wherein Lp and Lc are each independently selected from the group consisting
`of the structures of LIST E as defined herein; wherein:
`Tis selected from the group consisting of B, Al, Ga, and In;
`
`each of Y! to Y"is independently selected fromthe group consisting of carbonand nitrogen;
`Y’ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C=O, C=S8, C=Se, C=NRe, C=CReRs, S=O, SO2,
`P(O)R, CReRe SiReRr, and GeReRr,
`Re and Re can be fused or joined to form a ring;
`each Ra, Rp, Re, and Ra independently represent zero, mono, or up to a maximumallowed numberof substitutions to its
`associated ring;
`each of Rai, Roi, Ret, Rat, Ra, Rp, Re, Ra, Re and Rr is independently a hydrogen or a subsituent selected from the group
`consisting of deuterium, halide, alkyl, cycloalkyl, heteroalky1, arylalkyl, alkoxy, aryloxy, amino,silyl, germyl, bory],
`alkenyl, cycloalkenyl, heteroalkeny], alkynyl, aryl, heteroaryl, acyl, carbonyl], carboxylic acid, ester, nitrile, isonitrile,
`sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; the general substituents defined herein; and
`any two Rai, Roi, Rei, Rai, Ra, Ro, Re, Ra, Re and Rr can be fused or joined to forma ring or form a multidentate ligand.
`The compound of any one of claims 23-28, wherein Lp and Lc are each independently selected from the group consisting
`of the structures of LIST F as defined herein. wherein:
`Ra’, Re’, and R.” each independently represent zero, mono, or up to a maximum allowed numberof substitutions
`to its associated ring;
`each of Rai, Rei, Ret, Ra, Rp, Re, Rn, Ra’, Ro’, Re’, Ra’, and Re’is independently hydrogen or a substituent selected
`from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalky], arylalkyl, alkoxy, aryloxy, amino,silyl,
`germyl, boryl, alkenyl, cycloalkenyl, heteroalkeny1, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,
`isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, sclenyl, and combinations thereof, and
`any two Rai, Roi, Rei, Ra, Re, Re, Rn, Ra’, Ro’, Re’, Ra’, and Re’ can be fused or joined to form a ring or form a
`multidentate ligand.
`The compound of claim 12, wherein the compound has formula Ir(La)s, formula Ir(La)(Lex)2, formula Ird(La:m)2(Lex),
`formula Ir(.a)2(Lo-), or formula Irda)2(Lcy-1),
`wherein La is according to any one of claims 1-22;
`wherein cach Lex has the structure as defined in LIST G herein;
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`

`31.
`
`32.
`
`33.
`
`34.
`
`Ww a
`
`37.
`
`Attorney Docket No. UDC-1712P (376.0047P)
`
`R201
`
`R202
`
`; and
`
`_0=
`
`“Oo
`
`R201
`
`202
`
`R°*
`
`.
`:
`, wherein for each Le in Leys and Ly-u, R2°! and R2are each
`
`:
`wherein each Lchas a structure based on formula
`
`” “ O —
`
`“O
`
`each Lc. has a structure based on formula
`independently as defined in TABLE2 herein;
`wherein R”! to R??** have the structures as defined in LIST H herein.
`The compoundof claim 30, wherein the compoundis selected from the group consisting of only those compounds whose
`Lu« correspondsto one of the following: Lei, Ls2, Leis, Le2s, Loss, Leivs, Leis, Lei22, Lei24, Leiz6, Lei2s, Lise, Leis2,
`Lei34, Lei36, Lei3s, Lp140, Leia2, Lei44, Leise, Leiss, Leico, Lpie2, Lies, Leics, Lei72, Lei7s, Le204, Le206, Le214, Le216, Le2is,
`L220, L222, L231, Lp233, L235, Lp237, L240, Lp242, L244, Lp246, Lzas, Le2s0, Lp2s2, Lesa, Le2s6, Lpzss, Lez60, Lp262 and
`Lx264, Lp26s, L266, Lp267, Lp26s, Le269, and Lp270.
`The compoundof claim 30, wherein the compoundis selected from the group consisting of only those compounds whose
`Lez corresponds to one of the following: Lei, Le2, Leis, Le2s, Less, Leios, Leiis, Lei22, Lei26, Leis, Lei32, Leise, Leiss,
`L142, Leise, Lei6z, L204, L206, Lezia, L216, Lzis, L220, L231, L233, Le 237, Le 264, L265, L266, L267, Le26s, Le269, and
`Lx270.
`The compoundof any onc of claims 30-32, wherein the compoundis sclected from the group consisting of only those
`compoundshaving Lc; or Lo-n ligand whose corresponding R?°! and R?°are defined to be one of the following
`structures: RP!, RD}, RP4, RDS RDI RDO DIT DIS D2 QD2 _DI7 RDO QDI PDA? RDA PDAs DAO YDSO QDS4 PDSS,
`RD58, RDS? R78 RDP RDS RDS7 RDSPDS RDB RDU QDU7 DUS PDIP RDI20 RDII3 RDIG4 QDIIS QDS RDI
`RP44RDS RDM6 RDIQDI DIS! QVIS4 QVISS DIG! QDII5 RDIV QVII3 R200 RV201 D206 QD210 D4 PDS.
`R216 R18 D219 QD20 QD227 QD237 RDA RD? RDS and RP246,
`The compoundof any onc of claims 30-32, whercin the compoundis sclected from the group consisting of only those
`compoundshaving Lce1 or Lg-n ligand whose corresponding R?°! and R?°are defined to be one of selected from the
`followingstructures RP!, RY3, RP*, RPS RLY RIV RbIT R22Qv4ss ASV QE RVIQVIUS QVIS3 QLBA QVIS5 QVI36
`RPRPA RPMS RDG QDM9 DIS DIS RDIS5 QD19 D193 D200 D201 RD206 RDUO RDA QDAS QD2A6 V8
`RP?19. RP220. RP227. RE237 REAL RD24 RPS | and Rd246
`The compound of any one of claims 30-34, wherein the compound is selected from the group consisting of only those
`compoundshaving oneofthe structures for the Lcligand as defined in LIST I herein.
`The compoundof claim 24, wherein the compound is selected from the group consisting of the structures of LIST K as
`defined herein.
`The compound of claim 23, wherein the compound has Formula IT:
`
`RF
`
`RA
`
`RB
`
`4
`aN -
`‘|
`\,
`oe Ke ed
`f
`Mo
`ds,
`my)
`X
`Ke Ne
`6
`ems
`Ne
`\u Lb E
`B
`Lg
`
`°
`
`RE
`
`wherein M is Pd or Pt;
`wherein moiety A comprisesat least 7 ring atoms;
`wherein M coordinates to ring A through a metal-carbene bond;
`wherein moieties B, E, and F are each independently a 5-membered or 6-membered carbocyclic or heterocyclic rings;
`wherein X! to X® are each independently C or N;
`wherein Z!, Z?, and Z> are each independently C or N;
`
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`

`Attorney Docket No. UDC-1712P (376.0047P)
`
`wherein each of L!, L?, L’, and L* is each independently a direct bond or selected from the group consisting of O, S, Se,
`NR, BR, BRR’, PR, CR, C=O, C=S, C=NR, C=CRR’, CRR’, SO, SOn, SiRR’, GeRR’, and P(O)R;
`wherein eachofa, b, c, and d is independently 0 or 1;
`whereina+b+c+d=3or4,
`wherein K!, K?, and K3 are each independently a direct bond, O, or S;
`wherein at two of K!, K’, and K3are direct bonds;
`wherein each of R4, RP, RE, and RF independently represents mono to the maximum allowable substitution, or no
`substitution;
`wherein each R, R’*, R4, R®, R®, and RFis independently a hydrogenor a substituent selected from the group consisting of
`hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalky1, bory], arylalkyl, alkoxy, aryloxy, amino,
`silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile,
`isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof,
`wherein any two R, R’, R“, R®, RE, and RF may bejoined or fused to form a ring; and
`with the proviso that L‘ is not cyclohexyl.
`The compoundof claim 37, wherein moiety E and moiety F are both 6-membered aromatic rings.
`The compoundof claim 37 or 38, wherein moiety F is a 5-membered or 6-membered heteroaromatic ring.
`The compound of any of claims 37-39, wherein moiety F is a 6-membered heteroaromatic ming.
`The compoundof any one of claims 37-40, wherein L? is O or CRR’.
`The compound of any one of claims 37-40, wherein L? is O.
`The compoundof any one of claims 37-42, wherein L* is NR.
`The compoundof any one of claims 37-42, wherein L? is NR andRis fused with Ring C.
`The compoundof any one of claims 37-42, wherein L? is NR and R is fused with moiety E to form a carbazole group.
`The compound of any one of claims 37-45, whereindis 0.
`The compoundof any one of claims 37-46, wherein Z” is N and Z?is C.
`The compoundof any oneof claims 37-46, wherein Z? is C and Z? is N.
`The compoundof any one of claims 37-48, wherein K!, K?, and K?are all direct bonds.
`The compoundof any oneof claims 37-48, wherein one of K', K?, and K?is O.
`The compound of any one of claims 37-50, wherein the compoundis selected from the group consisting of compounds
`
`having the formula of Pt(La:yy):
`
`
`
`LAIST 1 as defined herein,
`>
`fect from: the group cons
`wherein Lai
`wherein L, is‘selected from the group consisting ofthe:structures ogLIST Masdefined herein.
`wherein each R““, R®B, RE, RF, RX, RY, and R% is independently selected from the structures of LIST B as defined herein.
`The compound any one of claims 37-50, wherein the compoundis selected from the group consisting of the compounds
`having the formula of Pt(La’)(Ly):
`
`52.
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`121
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`

`Attorney Docket No. UDC-1712P (376.0047P)
`
` wherein La xs selected fromthe exons co
`
`55.
`
`56.
`
`57.
`
`;
`wherein L, is selected from the group consisting of the structures 9
`wherein », 0, p, Ss, t, and uw, are each independently an integer from | to 135 and m is an integer from 3 to 135, wherein RI
`to R135 havethe structures of TABLE3 as defined herein.
`33.
`The compound of any one of claims 37-50, wherein the compoundis selected from the group consisting of the structures of
`LISTPas defined herein.
`34.
`An organic light emitting device (OLED) comprising:
`an anode; a cathode; and an organic layer disposed between the anode and the cathode,
`wherein the organic layer comprises a compound according to any one of claims 1-53.
`The OLED of claim 54 wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-
`emissive dopant.
`The OLED of claim 54, wherein the organic layer further comprises a host, wherein the host comprises a triphenylene
`containing benzo-fused thiophene or benzo-fused furan; wherein any substituent in the host is an unfused substituent
`independently sclected from the group consisting of CnHonu, OCnH2nt1, OAn, N(CaH2nt1)2, N(Ari)(Ar), CH=CH-CnHani1,
`C=CCnHann, An, Ari-Ar2, CnHan-Ar, or no substitution; wherein nis from 1 to 10; and wherein Ari and Arare
`independently sclected from the group consisting of benzenc, biphenyl, naphthalene, triphenylene, carbazole, and
`heteroaromatic analogs thereof.
`The OLEDof claim 54, wherein the organic layer further compriscs a host, wherein host comprises at least onc chemical
`moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran,
`dibenzoselenophene, 54?-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene,
`triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-
`dibenzoselenophene, aza-5A?-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-
`deJanthracene).
`The OLED of claim 57, wherein the host is selected from the group consisting of the structures of LIST R as defined
`herein:
`The OLED of claim 54 whereinthe organic layer further comprises a host, wherein the host comprises a metal complex.
`The OLED ofclaim 54, wherein the compoundis a sensitizer, and the OLED further comprises an acceptor selected from
`the group consisting of a fluorescent emitter, a delayed fluorescence emitter, and combinationthereof.
`A consumer product comprising an organic light-emitting device (OLED) comprising:
`an anode; a cathode; and an organic layer disposed betweenthe anode and the cathode,
`wherein the organic layer comprises a compound according to any one of claims 1-53.
`The consumerproduct of claim 61, wherein the consumerproduct is one of a flat panel display, a computer monitor, a
`medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a
`fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a
`personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a
`micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a
`video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
`A formulation comprising a compound according to any oneof claims 1-53.
`A chemical structure selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule,
`wherein the chemical structure comprises a compoundaccording to any one of claims 1-53 or a monovalent or polyvalent
`variant thereof.
`
`59.
`60.
`
`58.
`
`6l.
`
`62,
`
`63,
`
`122
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`